Someone might jump in and say this is wrong, but I can tell you how I setup a Split Domain, similar to yours (old Postfix/POP3 server as primary, Zimbra server as secondary). We've been running with this setup for almost a year, as we have been going through an extremely slow migration to Zimbra.
Keep you MX pointed toward your old server. The Zimbra install will complain that there are no MX records pointing to your Zimbra server, but you continue past this warning. You do need to have DNS, /etc/hosts, etc. all setup properly, but I've found no issues with not having the MX record setup for the Zimbra server. After the Zimbra installation is complete, on the Zimbra server execute the 'zmprov' commands outlined in the Split Domain wiki document. On your old email server use the transport file to direct email for the users you are moving to your Zimbra server. Your entries should look something like this:
jdoe@example.com smtp:[zimbra.example.com]
where jdoe is a user moved to the Zimbra server, and zimbra.example.com is the name of your Zimbra server.
After creating or modifying the transport file you must run 'postmap' against it in order to create/update the db file that Postfix uses (i.e. '/usr/sbin/postmap /etc/postfix/transport')
HTH
John