Most users would be too confused by it. undo/redo functionality would be better.
I don't see how it is confusing - however Windows doesn't have undo functionality in prefs either. AmigaOS has, by default, in all system Prefs apps, "Reset to defaults", "Last saved" and "Restore".
Most people I've worked with click "Apply" before clicking "OK", despite me saying the "Apply" step is unnecessary. The implication of the design is that "Apply" applies the settings and "OK" doesn't.
That's confusing. As is Microsoft's insistence on requesters that have "Yes" and "No" as an answer, resulting in long paragraphs of explanation as to what each does, when changing the button text would have been more logical for the user.
If you want different settings for different users then you should setup different users.
Agreed, for the scenario given, different user accounts is the correct solution.