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I have some heads that I bought from Puppetswar, and I'm curious if it's necessary for me to wash them? I've heard that that's a good thing to do for resin before using it, but is it necessary?

Never had a problem with Puppetswar, without washing.

The idea is that certain mold release agents will make paint not stick to the resin.

Yes it's necessary to wash!

I run a 3d printing business and I ship minis every day. While I wash and cure them before sending, there is still residue on them.

3d printing resin is UV curable and only really washes away with isopropyl alcohol. However, we wash in batches during larger printing runs. Meaning your mini didn't get individual care it needs. Both resin and IPA will deteriorate paint over time. Sometimes even making paint not stick at all.

Wash them 100% with IPA and a toothbrush.