I have a motorbike and wear my helmet about two hours every day, longer if I take a trip on it. It has never been painful.
It's snug and it can feel a bit weird the first few times (specially around the ears), but if you use a helmet and it hurts, I'd definitely get another helmet (hint: different brands have slightly different shells, so maybe try a few different makes).
I also have a GearVR and it took ages fiddling with the straps to get a comfortable fit. I can't use it for long, but it has nothing to do with pain: The phone I use gets very hot and it's so close to the eyes that gets uncomfortable. Also, the lenses fog up.