The cylinder head is the top part of the engine. It sits on top of the engine block. Where the two join there is a gakset. This is the head gasket. The head and block both need flat, straight, clean surfaces. If an engine has over heated the head can twist or warp (very very slightly, we are talking fractions of a millimetre). Or corrosion can wear away some of the face of the cylinder head. If either of these happen then you need to remove the head, clean it up and then cut a very small amount off the face of the clyinder head. This is called skimming, as the tool only just skims the surface being cut.
But you can use skimming to aid performance. If you skim a certain (calculated) amount off the head, when you re-fit the head the space that the air / petrol mix is compressed into (the combustion chamber) is smaller, and this means the compression ratio is higher, and as a general rule a higher CR gives slightly more power. But you must work it out, and you must not go too high.
So, there you are, two reasons for skimming. Cost for a light skim is about £30 ish.