You encounter the exact same compatibility issues you would on the web, with a somewhat slower uptake to new versions. Not ideal but entirely manageable.
> why would one want to use it
Primarily because (last I checked, anyway) any app using Electron has to bundle its own version of Chromium, which is massive. It also means each Electron-powered app is totally ignorant of the other, resulting in a lot of duplication and unnecessary memory usage. When you use the system webview you have minimal bulk and resources can be shared, as if they’re multiple tabs in one browser rather than each one being its own browser.