That would be extremely expensive just to make one head, even if you do get the cheap plastic. There are places that 3D print for individuals like Shapeways, but most 3D printers aren't big enough to make a shape large enough to put over your head, so you would probably have to go to a specialty place.
No, it's much more cost effective to just learn how to sculpt with clay and make a mold n' cast in foam latex if that's what you're going for, or just learn how to suit the original way.
No point is getting something printed in 3D just to to use as the skeleton. That's too much money to pay for something that you can do just as effectively using other materials, just takes more patience, but that's better than more money, yeah?