The Genesis' button layout was A,B,C arranged in a diagonal from bottom-left to top-right. A was usually 'accept'. The Dreamcast had a diamond with A at the bottom and B to the right.
Nintendo's Famicom buttons read A,B from right-to-left, and that trend continued with the Super Famicom's diamond, which had A to the right and B at te bottom. The N64 had a weird layout, but again B was to the left of A.
Sony probably focus tested the pad in the US and found that players were more used to Sega's layout.
My guess is that Sony thought that X and O wouldn't have as obvious connotations outside of Japan, and figured that people would assume the button closest to the player (X) would be the OK button. In practice, I have found that people with very little exposure to Japanese culture still have the same association with X and O in their heads and get confused when using Playstations ("you press X to accept???"), so I'll curse Sony forever for this stupid regional change.
That's not to say that those expectations weren't due to cultural differences.