Hi Chris_Huber
Thank you for your post. There can only be one default email used. These email settings apply to all emails sent on your behalf from MYOB. This includes invoices, quotes, and pay slips (payroll). What you can do is to customise your messages for Sales, Purchases, and Pay Slips. Go to Set Up >> Preferences >> Emailing >> Email Defaults. This Help Article, Set up your default email messages, has more information that you can use as a guide as well.
Please feel free to post again. I'm happy to assist further.
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