There is a Windows "native" 640x480 mode at 60p (non-interlaced) which you cannot edit - it is hardware locked. You'll only see it in ArcadeOSD if you have "Lock unsupported modes [no]" selected on the first ArcadeOSD screen. Normally you should select "[yes]" there.
All that's assuming you're actually using CRT_emulator and ArcadeOSD on a CRT. Maybe provide some more detail and/or screenshots. What monitor, graphics card you are using, what you've tried to do (and how, why). People won't respond if they are not sure exactly what your issue is.