Squats do it for me.
Squats are the time-honored way of training your gluteus maximus (butt). You can add resistance by performing them while holding dumbbells in your hands or with a bar across your shoulders. If you opt for the bar, make sure you have a spotter unless the resistance is very light.
Varying the width of your feet will change the emphasis of the exercise. The closer together your feet are, the more your quads (front of the thighs) will work. As you move your feet further apart, you'll feel the exercise more in your hips and butt. You should always have someone check your form to be sure you're doing squats properly. Lunges are another exercise that works the same area. If you go to a gym, the leg press machine may be easier to use than doing squats with a bar, and it attacks the same region.
Some people have complained that steppers make their butts bigger. I think those people are: a) Eating more than they think they are; and b) Not working as hard as they can. Nevertheless, if you use the stepper at a slower frequency and take honest, normal steps -- as opposed to leaning on the machine with your arms and staying on your tiptoes -- you can recruit those butt muscles too.
Any movement requiring hip extension will work your butt, and I think the best exercise of all for that is skating. Ever see a speed skater's butt? No other athletes depend on hip extension for propulsion as much as skaters do. They keep their upper bodies almost parallel to the ice (or road, if it's in-line skates you're talking about), and the push in the skate stride starts with hip extension and finishes with knee extension (quads). Skating is, in fact, not only a great butt exercise, but a great overall leg exercise, and that's why speed skaters have such nice lower bodies.
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