There are 2 spots for emails.  The one on the main AR tab could be your main order confirmation email and the one on the CONTACT tab could be the email for accounting.  That's how we do it here.  

There are 2 spots for emails.  The one on the main AR tab could be your main order confirmation email and the one on the CONTACT tab could be the email for accounting.  That's how we do it here.  

I believe Stacey is referring to From email addresses.

PrintBoss is really the way to go for this. However, you could also roll the dice with a MAPI compliant email client like Outlook. (Uncheck the "Use Email Service" checkbox on the Email tab of the Company Profile screen. That should try to send using Outlook to send the email(s), but Windows and/or Outlook might protest.)