I had tried them all (GF3, GF4Ti4600, R8500LE, R9700PRO), I have all the top end cards available (except Matrox Parhelia).
I have the popular DVD playback software (WinDVD 4, PowerDVD XP 4.0), and have spent many hours watching many DVDs on my PC (well, it is my room entertainment system) with them.
The difference is there, ATI is definitely better than GF3/4 when hardware acceleration is on, I have mentioned before that GF3/4's motion compensation seems broken in my experience, software playback is better than hardware on GF3/4. Without hardware acceleration, it is up to the 2D and scaling quality of the display cards. But I can tell you that when hardware acceleration is on, the difference between R8500/9700PRO and GF3/4 are bigger than without.
I use 2 displays, Compaq P110 21" CRT monitor and a Hitachi 15" LCD panel.