You'll actually want to go Start > Control Panel > Mail. I'm not sure why it would mention User Accounts in there, as there is no link to the Mail settings from User Accounts.
Once clicking on Mail, you'll want to click on the Data Files button. There you should see a list of the data files being used. I'm guessing that the default will be the Exchange .OST file that didn't get properly populated. You'll want to click on the .PST file associated with the email account you want to keep, and click "Set as Default". You should probably remove the .OST file for your Exchange account as well.
Hope this helps.
-SW
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