Rest assured that while CDPR/GOG may be content to rest on the Laurels and Hardee's while the world passed them by, Valve has no such qualms and even if intentionally or otherwise, they will be making as may titles as capable on running on the deck as humanely possible.
Here are two easy things:
1) Dobox is Dosbox, it'll run no matter what since there's a native version. This even includes games which inexplicably have Windows only installers but are pure DOS.
2) ScummVM is ScummVM, it also has a native version.
Now the less easy things:
3) Most 2D indie games should run fine via Proton. Especially games that draw to things like the SimpleDirectLayer.
4) Many games have source ports which are coded to natively run on any system. Such as OpenTTD, OpenRCT2, and eDuke.
Harder things:
5) 3D accelerated games are going to be a gamble. You'd think Serious Sam 1 would run as free as it gets, but it doesn't know what the hell Vulkan is. And for games that were made during the protocol wars,
GOOD LUCK. 6) 32 bit library support is being taken out of many distributions or retired; which means that some games just aren't going to work right. There's even a few games here on GOG that are distributed with broken library files.
There are many factors including an irreversible bug which make it simpler to retire these instead of keep supporting them.