Hi
Inbound = traffic entering the pix
Outbound = traffic leaving the pix.
So if your users are behind the inside interface and your mail server is on the outside you could either do an inbound access-list on the inside interface or an outbound access-list on the outside interface. Generally speaking you would block it on the inside interface to stop the traffic having to go through the pix just to be dropped before it leaves the outside interface but there are times when an outbound list is useful
** Edit
example of where you may want an outbound acl in your situation
if the mail server is sitting on a separate DMZ all by itself and you don't want to apply an access-list on the inside interface which might disrupt other traffic you could apply an outbound acl on that DMZ interface. **
Note that you can only do outbound access-lists on a pix from v7.0 onwards.
HTH
Jon