From Heinz Tschabitscher,
Your Guide to Email.
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I have more than one email address. Some are just for sending, not for receiving mail (they forward to other accounts, for example), so there's no point in setting up a separate account for each of these addresses in Mac OS X Mail. Fortunately, I can use more than one From: address with an account.

Use Multiple From: Addresses with a Mac OS X Mail Account

To set up multiple addresses for one account in Mac OS X Mail:

• Select Mail | Preferences... from the menu in Mac OS X Mail.
• Go to the Accounts category.
• Highlight the desired account.
• Enter all email addresses you want to use with this account in the Email Address: field.
  • Separate the addresses by commas (like "me@example.com,­me_the_pro@example.com").

After you have closed the configuration dialog and saved the new settings you can send mail from all these email addresses.

Additional Addresses Disappear When You Relaunch Mac OS X Mail?

Unfortunately, you cannot add alternative addresses to .Mac email accounts in Mail. You can, however, set up your .Mac account as an IMAP account (use "mail.mac.com" as the IMAP and "smtp.mac.com" as the SMTP server as well as your .Mac user name and password) and add alternative addresses to that account.