zmmtactr start is what starts the mta and begins the main.cf rewrite
you can watch this by doing a
#tail -f /var/log/zimbra.log
also other useful log files would be in /opt/zimbra/log/ as it doesn't keep everything in /var/log
Im using Deb 5 so it may be different for you. I would check /etc/groups to insure the group is not messed up, fix that and try to chown the files to root

ostfix and then do a restart
hope this helps.