The difference is that the muscles around the eyes move more in real smiles.
Telling Lies is a good book for understanding the muscles in the face and how to tell a fake smile or frown from a real one.
For the smiles, its generally the crow's feet at the corners of the eyes -- there is a type that is impossible to generate unless you are really smiling due to an emotion, as you can't control those muscles voluntarily. Really neat stuff, but a little frightening when you start paying attention to people in your day to day activities.