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Uncle Rico is most definitely the shadow because he keeps coming into Napoleons life and saying that Napoleon can't do anything. The villain at this point of the story is Summer because she is running against Pedro and trying to win. One of the tests and trials is the beating of the pinata. Pedro then learns that you can't make, and destroy a pinata of the person you are running against.
Another test at this point of the story is when Napoleon goes on stage and helps Pedro with his campaign. Napoleon can be both a hero and a mentor because he was willing to go out and show the world what he's made of. When Napoleon wins the election for Pedro that is when he is "resurrected" and starts on the road back(quite literally). The enlightened state is when Pedro is at the picnic with his family and Napoleon plays tether-ball with Deb and they are all enlightened and prepared for the year to come.
Napoleon Dynamite was one of the funniest movies I've seen, but it is full of the hero's journey and that's what makes it so great to watch.