Not to gloat, but i have a very good amount experience in the subject.
For starters, be sure to have the right tools. When i first started, I just used my regular printer with regular printer paper and i cut everything out with scissors and i put all the tabs together with tape. Not even double sided tape, just regular tape, But i learned from that. DO NOT DO THAT.
Just start with a good exacto blade, and some scissors for the longer lines that need to be cut, but mainly an exacto blade, some extra blades, because eventually your blade will get dull even from cutting paper. Along with the exacto and some spare blades, buy a cutting board, i made the mistake of cutting my pieces directly on my kitchen counter and it left some marks... oops... And for the adhesive that binds the tabs together, some people like to use hot glue because its easy to bend if you need it to bend, but i find its too thick, so i use super glue most the time, super thin, and easy to use in small doses. But if you are working on a larger project, than you might need a few things of super glue. And now, i like to print my stuff at FedEx Kinkos on European cardstock paper. Its wider, longer and thicker. Like i said, i use to print on my own paper at home and it was often too small and the lines would go off the paper leaving me with an inaccurate paper model. And last but not least, you will need the program "Peakura Viewer". Its a free program and allows for minor editing if i remember correctly, but you cant make a pep file in the program.
And to answer your initial question, i believe Fet's Helmet wouldn’t be too bad of a place to start only because its mostly just rounded edges, no random curves or divets or indents. So you shouldn’t have too much trouble with that at all. And the files themselves are mostly free. Some people make the pep files and sell them, but mostly you can find whatever your looking for for free,
This is a good place to start, this guy sells some of his files, but also has a lot of them up for free. In fact, he even has the boba fett helmet about halveway down the first page and its a free download.
http://www.therpf.com/f24/fierfeks-star-wars-pepakura-file-development-122071/
Hope this helped.
. I was wanting to make a few starwars lids, was thinking of starting with fett? Is that a decent project to start with? Are there any helpful guides/videos I should take a look at before starting? Iv havent had any experience with pep before, are the files widely available/free and do they need altered? Sorry for all the questions and thanks in advance for any advice 
