Fiberglass and bondo is the go-to method because it's so tried and true. It gives amazing results on a very short budget (You can make a helmet for about 40 bucks when you nail the technique down), results that come close to machined pieces, and it can be incredibly strong (this is the stuff they make boats out of). There are some people at the TechShop who are going to be 3d modeling, MakerBot Routing, and then vacuum forming some armor soon. Sure it gives you perfect symmetry and cuts down working time but... You DO need that multi-thousand dollar makerbot, a high quality, large vacuum forming table, and quality 3d modeling software...
As for alternatives within the realm of hand-making armor, there are plenty of things out there. Spray urethane is similar to plasti-dipping that foam armor uses. The reason why people will go pepakura is because, once you pour the rondo inside the helmet, you can do a LOT of post modifications to the helmet. A lot of the files are rather low-def, even ones ripped out of Reach, and so things like vents, detail lines, and even custom mods, require you carve into the piece, and really spray-ons aren't going to give you the thickness required to do that. If you are okay with how a pep piece looks after you assemble it, go ahead and spray on a finish, it might be strong enough but I can't say personally. If the blockiness and lack of detail bug you, then you're going to have to use rondo. It's really totally up to you how you wanna try it. Someone on this site layed kevlar instead of fiberglass inside his ODST piece. He made a bullet resistant chest plate! It looked pretty bad, but it was actually stopping pistol rounds.
We won't discourage you experimenting, it may work for you, it may end it horrible failure, it's hard to say! The bondo/pep method is born out of trial and error (that's what birthed rondo actually), so it's always good to try new things to see what you can do, just prepare yourself for some failures on the way, it's part of inventing! If you'd prefer a safer route, bondo and fiberglass. Good luck either way!