is too broad. In general I would say that the newer Samsung LCDs are better than the newer Sony models. Having viewed the XBR4 and the Samsung 71F series side by side, both hooked up to a stand alone Blu-ray player via HDMI, playing a Blu-ray movie, I can honestly say that it is no contest. The Samsung was in another league. But these are top of the line 46" models. This does not mean that the 32" models that you are comparing will yield the same results. Without knowing the model #'s it would be impossible to say which is better. I know you said they have the same specs, but lots of TVs have the same specs and still perform differently. Samsung has recently become the king of LCDs, so depending on how old the models are that you are looking at, the Sony may or may not be better.
This may sound snobbish but if you are getting a 32" TV, price might be the reason that you are going so small. If that is the case, without knowing the models in question, I would say that you would be better off going with the cheaper one. You will still be getting a TV from one of the two best LCD manufacturers out there. And at 32", if I can be so smug lol, dare I say the slight picture differences between the two sets will not be a major factor anyway. So why drive yourself crazy.
If you have the budget and space, I would suggest getting at least a 50" set if you plan to watch movies and you sit a normal distance from the screen. 32" is really tiny. It becomes about a 27" when you watch a movie with letterbox bars on the screen. And yes, a widescreen TV will still display many movies with letter box bars. Movie widescreen and TV widescreen are two different things.