Is POPFile capable of doing SSL email connections?

Yes, 0.22.0 (or later) supports SSL connections between POPFile and the email server.

See Can I use POPFile if I want to use SSL connections to my server? for details

The following applies to earlier releases:

Due to the nature of SSL it isn't possible to do this directly as POPFile can't see the encrypted data between your email client and server. At some point in the future it might be possible to do if someone were to implement an SSL proxy module for POPFile. Some users have worked around this by using Stunnel with POPFile. Read this Howto article for configuration information.