well, first of all, what version of outlook are you using?
If you are using outlook 2000 I believe you can go to tools, accounts, (same as OE) and add a new account.
I have been using outlook 2002 for a while now and cant remember 2000 that well. In 2002 you go to tools/email accounts and select add.
I think in bother versions you can get to the accounts from tools/options and mail settings.