You might find the Beginner's Introduction to POE over at perl.com useful.

For me the best way to learn more about POE was to just start using it. In many ways it's very different from other styles of programming and can take a while to get used to. But once you get the hang of it you'll never look back! I also found the POD included in the modules to be fairly well written and just taking the time to sit down and read through it helped a lot.