It's actually a lot easier than you think. I could teach you the basics of PS layers in less than an hour. Actually, learning the ABCs of PS isn't hard at all. What is confusing and daunting is the sheer number of different tools, effects, filters, and functions that PS offers. I've been using PS more or less every day for well over 20 years, and there are still functions that I either don't really understand, have rarely or ever used, or don't even know exist!