Here you can find a details explanation and a solution:
http://www.slipstick.com/outlook/outlook-2010/multiple-accounts-and-the-default-account/
(currently down, you can use Google Cache: http://webcache.googleusercontent.com/search?q=cache:2_1XlzFA6qIJ:www.slipstick.com/outlook/outlook-2010/multiple-accounts-and-the-default-account/+&cd=1&hl=de&ct=clnk&gl=de)
a) Registry key in Outlook 2010 SP1 and Outlook 2013
When you have multiple accounts and an IMAP account in Outlook 2010/2013 and you change the default sending account to the IMAP account, you may experience the following issues:
When you click a mailto link from a browser or from Outlook, the default sending account is the Exchange Server account instead of the IMAP account.
When you create a new email message, the Exchange Server account is selected instead of the IMAP account.
Out of the box, Outlook 2010 SP1 and Outlook 2013 use the default account for Send to commands but not for new messages created while viewing a pst file (when a POP account is assigned to the pst file), unless you set a registry value to always force the use of the default account.
To force all new messages to use the default email account, regardless of which pst file you are viewing, browse to the following registry subkey in Outlook 2010 and add a DWORD named NewItemsUseDefaultSendingAccount:
HKEY_CURRENT_USER\Software\Microsoft\Office\14.0\Outlook\Options\Mail
DWORD value: NewItemsUseDefaultSendingAccount
Value: 1
In Outlook 2013, the key is:
HKEY_CURRENT_USER\Software\Microsoft\Office\15.0\Outlook\Options\Mail
DWORD value: NewItemsUseDefaultSendingAccount
Value: 1
b) Registry key to force account selection every time
This fix is simple, but can get annoying, fast, since it forces the user to select an account every time they send a new message. (Replies and Forwards always use the account the message arrived on.)
This might be good for people who use multiple accounts and frequently (accidentally) send using the wrong account, especially if they are sending sensitive documents, as it will almost eliminate accidentally sending email from the wrong account.
HKEY_CURRENT_USER\Software\Policies\Microsoft\Office\14.0\outlook\options
Value Name: ForceAccountSelection
Value type: REG_DWORD: 1 for force, 0 to disable.
In Outlook 2013, the registry key is:
HKEY_CURRENT_USER\Software\Policies\Microsoft\Office\15.0\outlook\options
Value Name: ForceAccountSelection
Value type: REG_DWORD: 1 for force, 0 to disable.
Notes: You need to create the path if it does not exist. You can also set this using the Office 2010 group policy templates.
The value type is the same for both 32-bit and 64-bit Outlook.
What are .ost and.pst files?
Outlook Data Files (.ost) are used when you have an Exchange account and want to work offline or use or use the default Cached Exchange Mode. This type of data file is also used for accounts that you set up with the Outlook Connector for Outlook.com (formerly Hotmail). Outlook Data Files (.ost) are always copies of items that are saved on a mail server and don’t have to be backed up like Outlook Data Files (.pst).
Source Introduction to Outlook Data Files (.pst and .ost)
My computer seems to lack .pst files.
"4 (of 5) email accounts are @outlook.com, and are listed as 'Exchange ActiveSync', under 'Type'. However, these 4 are all personal accounts on my personal computer. They don't concern any servers or administrators.
1 (of the 5) is my work email, and is listed as 'IMAP/SMTP'."
This confirms that your email is using Microsoft Exchange (in the case of your work IMAP/SMTP account). The .ost
files are from accounts that you have set up with the Outlook Connector for Outlook.com (formerly Hotmail).
Outlook Data Files (.ost) are always copies of items that are saved on a mail server and don’t have to be backed up like Outlook Data Files (.pst).
The adminstrator of your work Exchange Server (in the case of your work IMAP/SMTP account) should be responsible for backing up the server (and your emails).
You might like to confirm with them that backups are actually taking place.
For the other email accounts @outlook.com then Microsoft is the administrator of 'your email server'
Do I need to backup an .ost file?
Some accounts use an offline Outlook Data File (.ost). This is a synchronized copy of the messages saved on a server and that can be accessed from multiple devices and applications such as Outlook. These accounts include IMAP, Microsoft Exchange Server, and Outlook.com accounts.
Offline Outlook Data Files are saved in
drive:\Users\user\AppData\Local\Microsoft\Outlook
.
It isn’t necessary to back up an offline Outlook Data File (.ost) as it is a copy of the information on the server. If you set up the account again or on another computer or device, a synchronized copy of your messages are downloaded from the server.
Source Create an Outlook Data File (.pst) to save your information
But I really want to backup these 4 .OST accounts
In this case you might like to backup the local .ost
files using your normal backup program (or trust Microsoft not to mess up your accounts)
You can also export your mail as a .pst
file by following the instructions in Exporting and Importing Mailbox Content in Outlook 2013.
The .pst
file can then also be backed up using your normal backup program.
The advantage of using a .pst
file is you can then import all of your email to another computer running Outlook.
Note:
If you access your email account from multiple computers or devices, it’s important to know that when messages are moved to an Outlook Data File (.pst) they are available only on the computer where the file is saved.
Clarifications as per your comments.
You wrote Microsoft Exchange (in the case of your work IMAP/SMTP account). Does this mean a Microsoft Exchange account that also runs on IMAP/SMTP?
Microsoft Exchange can be configured to support IMAP/SMTP. It could also be some other mail server that supports IMAP/SMTP. Only your work IT department can answer this question.
How do I backup .ost files? Do I just copy and paste them onto backup storage (ie an USB, external hard drive)?
You can copy and paste but it is better to use a scheduled windows backup.
It’s important to know that when messages are moved to an Outlook Data File (.pst) : How can email messages be moved to a .pst?
Email messages will be moved if you create a local archive, and drag and drop emails into the local archive.
You can configure Outlook to automatically move your emails to the local pst
file if you wish. See How to Automatically Move Mails From Outlook to PST.
Note:
If you export your mail from .ost
to .pst
you are creating a copy of your email not moving it.
Further reading
Best Answer
I had this problem as well, I fixed it by removing the "Generic Credentials"
You can do this by going here: Control Panel\All Control Panel Items\Credential Manager
Then delete all the items listed under "Generic Credentials" by pressing the down arrow off to the right, then "Remove from Vault" starting from the top most crednetial.
Then press "ok" in the password prompt and you should be all set