I've been working on my web design skills for the past month. Not my web programming skills, but the design work itself. If I want something centered, or a certain width, or to access a database, I can do that in multiple languages. But what should the application wear? Is it a high-heel and little black dress application? Hard hat and blue jeans? Naked with red lipstick? I'm not very good at dressing them yet, and I'm realizing my weakness when working with my students, because they ask me questions about it all the time.
My first realization was Don't center. Centering is the first impulse when doing web design for some reason and it is almost always wrong. It's what you do when you don't know what to do.
A person's eye tends to start at the top left (or right for some languages), so that is where the most important things should be, not the top middle. Reading is also easier if the left margin is consistent. Designs that are centered are harder to read, and because there is not a consistent margin on either side, it tends to look messy.
For a great introduction to design, use this book:
Non-Designer's Design Book by Robin Williams. It might not be for the web, but the concepts in it work for web design.