I think Cupra_power may have been kidding...
If you know the swept volume (easy enough - divide engine capacity by no. of cylinders, so for a 4 cyl VAG 2.0 it's 1984cc/4 = 496cc) and the original compression ratio, you can work out the size of the combustion chamber before the skim. Compression ratio is (swept volume + combustion volume)/combustion volume. If you then measure the size of the combustion chamber after the head has been skimmed and rebuilt, then you can work out the new compression ratio as swept volume won't change.
(edit) to answer the question about octane, no, you probably won't need to change from whatever fuel you're using at the moment so long as the compression ratio doesn't change from say 10:1 to 12:1. Check with your engine man about how much is going to be skimmed off. 4mm sounds ridiculous (was half asleep when I posted earlier...)