Upgrade path – Oracle Standard to Oracle Enterprise

As @ik_zelf mentioned, your PATH variable will need to include the "bin" directory of your Oracle software install. This will allow you to execute commonly-needed commands/utilities like "sqlplus" and "lsnrctl" without changing directories. This is typically $ORACLE_HOME/bin

Your TNS_ADMIN variable needs to be set in a similar matter, pointing to the location of your tnsnames.ora, listener.ora, etc. By default, SQL Plus checks this directory (defined by TNS_ADMIN) for tnsnames.ora. This is typically $ORACLE_HOME/network/admin

If you want to connect to your database via TNS, your tnsnames.ora file (assuming a ORACLE_SID of "myDatabase", a host of "myHostname" and the default port) would look something like this:

myDatabase = 
    (DESCRIPTION = 
        (ADDRESS = (PROTOCOL = TCP)(HOST = myHostname)(PORT = 1521))
        (CONNECT_DATA = (SERVICE_NAME = myDatabase)))

This would allow you to connect locally simply by doing the following from a command line:

sqlplus username/password@myDatabase

Of course, as SQL Plus looks for the tnsnames.ora file in the location defined by $TNS_ADMIN, this will only function locally. To access this database via TNS (Transparent Network Substrate) from a remote machine, you would have to install the Oracle client and ensure that the TNS entry for myDatabase (as described above) is included in the remote machine's tnsnames.ora file as well.

Here is the Oracle 11.2 installation document describing the administrator user accounts after installation. Once logged in, you would change passwords with the syntax

alter user system identified by mynewpassword;

Note the SYS and SYSTEM accounts are assigned the DBA role. The DBA role does not have a password, the accounts do. The DBA role is created with every installation. You could grant the DBA role to another user if needed.