It depends on your iTunes preferences.
1.If iTunes is running default, iTunes actually copied all that media to your local drive, and you would have to delete it manually via sorting by "Date Added" to remove it.
2.If you have iTunes set to reference the files, when you disconnect the drive iTunes has some pretty annoying behavior where it will try to maintain the link but it will become a ghost music icon, the best way to get rid of these is sort by "Date Added" in your library and remove them manually.
These behaviors can be checked under iTunes preferences, I copied this pic from the Apple support site under HT1751:
I can answer the second part of your question. Since you just updated the MacBook's iTunes settings to point to the NAS, it's iTunes library file still resides on the MacBook. This is a .itl file in your ~/Music/iTunes folder.
iTunes relies on this database to tell it what's in the media folder. If you add stuff to the media folder without adding it through iTunes (i.e. just dropping files in Finder, or using another copy of iTunes on another machine) then that .itl database does not get updated.
So when you add files through iTunes on your Mac Pro, it updates the .itl database on your Mac Pro, but not your MacBook, so the MB can't see those files. If you add anything through iTunes on the MB, the Mac Pro database won't have it, since the copy of iTunes that connects to that database did not process the files.
I have a similar setup to what you're doing: iTunes media on an external drive connected to my iMac, and a MacBook which I use ONLY Home Sharing on.
You might get the idea to move one .itl file to the NAS and open it in iTunes on both machines, and this will work, but you can/should never have it open in both at the same time. That .itl file is really just an SQLite database, and they don't allow simultaneous access, so I've never even attempted this.
With respect to your first question, check ~/Music/iTunes and see if there are any old library (.itl) files. It's most likely that iTunes is opening an old copy or a backup of the database. If you duplicated the database or started a new one before moving your media, this might be the cause.
Start iTunes and make sure the media folder is set correctly or make some other change in iTunes. Now go to ~/Music/iTunes and look for the .itl file that has most recently been modified. Move all the others out of the folder.
Quit iTunes and restart it while holding the Option/Alt key. This will bring up a dialog that lets you select which database to use. Select the .itl file you left alone and it will continue using that as the default library.
Best Answer
Indeed, the only folder that iTunes uses to look for media by default is iTunes Media.
However, that doesn't mean that you can simply delete those other folders. You might be referencing files from those folders in your iTunes library. Check those folders for music, and only if there's no files you need in there, then delete them.