i know certain games don't work or are more prone to be buggy running in a 64bit OS which is why i ask.

if there are certain GoG games that don't work in a 64bit environment, it would be nice to see that under the compatible list of OS

I think they should all work. The only 16bit games that I know of are ones that are running in DOSBox and DOSBox itself is capable of running on 64bit versions of Windows.

Typically it's the installer programs thare are written in 16bits and won't run, but the games are usually 32bit.