Yes, POPFile is capable of communicating with multiple email servers and clients. POPFile is typically set up to classify email for any email accounts you access.
Normally POPFile will access one email account at a time (as most email clients do as well.) If you need to check multiple accounts simultaneously, you can enable this feature on POPFile's configuration page by changing “Allow concurrent POP3 connections” from “No” (the default) to “Yes”.