Outlook provides only one Exchange account per Outlook. If you need to use several addresses (in the from field, say, john.doe@example.com and webmaster@example.com), you may want to see this thread. Basically, add an IMAP account (how elegant..) with identical info as the Exchange account.
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Multiple Sender Addresses For Outlook
03-Oct-08Enter multiple addresses in the Email Address field of your Mail.app Account Information dialog, separated by comma. Works flawlessly. This has been bothering me for years. I didn't know how to do this until Justin showed how!