If you want to know whether or not a particular game runs on Windows 10, just check the "Works on" section on the right side of the game's page. Should you run into problems getting it to work even though it's listed as compatible with your system, and the support team is unable to fix your problem, you can request a refund within 30 days of purchase.
When it comes to old games that were originally released for DOS, you can be pretty certain they'll run flawlessly on modern systems, thanks to the inclusion of a program called DOSbox. It's usually just the Windows games from the late 90s and early 2000s that pose problems in that area.
And here are all the games that are currently supported for Win10:
https://www.gog.com/games?system=windows_10&sort=bestselling&page=1 Support is generally alright, although they used to be significantly better.
If a game seems too pricey to you at the moment, you can always wait for it to get a discount at some point in the near future, as there are frequent sales and promos like this one:
https://www.gog.com/promo/20161014_weekend_promo_retroism_wargaming_majesco