Whoa, I said plaster of paris is a bad idea. Plaster of paris is too soft for molds. Go to www.usgypsum.com to learn more about different types of plaster.
Plaster is cheap and its easy to work with. It is also not as toxic as polyester resin. It wouldn't be a bad idea to make a few "test molds" before risking your prized fett helmet that you just spent all that time on. If you build yourself a 1/2 sized fett helmet, (accuracy non-issue) you could make a practice mold if it at very little cost, but you would learn a lot from the experience. You can even practice your hand at fiberglass before tackling the big project.
Good molds don't happen by accident; they come from practice and experience.
A fiberglass mold would use the same principles, but is a lot more work. Try the plaster mold first and a fiberglass one after you have worked with the material for a few trys.