Well well well.. after a
lot of digging, we found that a rule in the firewall caused this. SMTP ALG (Application Layer Gateway) was enabled, and the rule for Anti-SPAM,
'Deny emails with mismatching SMTP command "From" address and email header "From" address' was enabled.
I'm glad we got this sorted; but I'm confused as to why it works with the Zimbra default domain
Oh well.. on with the evaluation! Thanks for the help!