Whenever I had "hacked" websites on my server, attackers got notice of ftp-user-accounts and abused them. So they uploaded php-scripts using ftp, which were executed by an http-call thereafter and deleted subsequently. So keep a look at proftpd's logfiles and change user-passwords if necessary. One thing to keep in mind: you cannot be sure, that spamming-scripts relay mails using postfix. Some of them got an own smtp-engine so you probably don't even notice these mails. Thats why on my system, only the postfix-user is allowed to communicate with foreign hosts with destination port 25.
If I'd start the webhosting-business again from scratch, I'd additionally implement the configuration from Nuxwin's previous post. Unfortunately I didn't enforce this in the very beginning. So now, with hundrets of domains running, I cannot simply change this, because my client's websites rely on "trusted localhost". That said: by enforcing client-authentication (postfix) in parallel with the firewall-thing described above, you can almost certainly be sure, that your server will not be abused by spammers. Exception: attackers get notice of mail-accounts of your clients...
To explain this what is happening on your server...
In general, there are two way of sending mails using php:
a) The function mail(), which is an integrated part of php. By disabling this function using php.ini, you can prevent users to use this way of sending mails.
b) You code an own mail-engine using php - this is especially the case when using phpmailer. This framework doesn't rely on mail(), so disabling the function doesn't affect this. And as I said above: these engines doesn't use postfix necessarily...