I made plenty of mistakes when starting to work with fiberglass. Still do. But nothing has sank yet. Some of it was too heavy, too light, didn't look as good as it should or took a lot more work than it should have get it looking good. Like Mike said, it comes with practice. If you screw up there's always sandpaper.
Having a couple different hardeners on hand is nice so you can determine how quickly the resin will kick. When I get stuff from Raka I order fast (around 8min. pot life) and slow (around 20 minute pot life). I can mix these to get anything I want in between. It's nice to use the fast setting stuff when it's colder in the shop and you only have a small project and the slow is nice when it's warmer or you have more work to do. I've recently started using Adtech and their slow hardener has a 45 minute pot life, which is great when doing an entire boat. Much less stressful.
Peel ply does make a huge difference. I peeled it off the stems of my composite build this morning and while there are a few pockets of unfilled weave where the peel ply puckered because of the tight curve for the most part it's got a near perfect finish that will only require a little sanding and another light coat of epoxy to finish it off. The transition from the newly added cloth to the hull is nicely tapered with no edge. Without something like peel ply it would have taken 3-4 more coats to fully fill the weave and then sanding on top of that.
Another tip for working with fiberglass is that you can do a lot of easy work with a sharp chisel, scraper, or knife when the epoxy is mostly setup but still 'green'. At that point it's pretty much set, maybe you can still dent it with a thumbnail, maybe not, but it's not really hard yet. When it's like that you can easily shave off drips and runs or trim away any extra cloth that might be hanging over the shear line with a razor blade knife. Soft enough to cut but hard enough the cloth won't move. Much nicer than sanding it off later. The 'green' time is usually a pretty wide window (a few hours) depending on ambient temp, speed of the hardener, and how much resin was applied (thicker laminate=more resin=more heat=faster setup).
Alan