I do a lot of work in Photoshop, and tend to listen to podcasts (including Night Vale) while I do that. They're also nice to listen to while doing household chores or yard work.

I would try a few of the more stand-alone episodes. "Summer Reading Program," or "Sandstorm Part A/B" are both entertaining and don't touch on too much of the ongoing plot threads. "Cassette" might also be fun as it involves some creepy backstory for Cecil.