Unfortunately, a Start button can only be animated on the mouseover state, so you can't have an animation when it is idle or pressed.
As far as image states go, it's Normal, Pressed, Disabled (never used afaik), Mouseover, Default (also never used). After that, you can add any animation frames for the mouseover state.
So, if your animation is 6 frames, for example, the first 5 frames would be the regular button states, and the following 6 would be your animation. I always use a copy of the first frame of my animation as the mouseover state image.
In the animation settings in SkinStudio, you would tell it to start the animation on frame 5 and end on frame 10. You might be asking yourself, "why doesn't it start on frame 6 and end on frame 11?" That's because the first frame is considered frame #0. So the 6th frame is actually frame #5, etc.
I hope that helps a bit. 