Ohhhhh. . .NOW I get you! The issue is that Zimbra does not install Postfix in the usual spot. ALL of Zimbra's programs are under /opt/zimbra; in the case of Postfix the path is /opt/zimbra/postfix. Without changing your paths, neither Webmin nor Asterisk is going to be looking where Zimbra's postfix installation is looking.
I'm a little surprised you even have a /var/spool/postfix. Did you perhaps have another installation of postfix (independent of Zimbra) on this box before doing the Zimbra installation? Two competing copies of the same program could create all kinds of joy for you. . .
Does Asterisk have to send messages by dumping them in a spool folder, or can it send them to an SMTP port? If the latter, just route it to your Zimbra localhost address. If the former, since I'm no postfix expert I won't comment, but I imagine it's possible once you have the correct paths.