The only real way to get used to a peripheral or controller is to use it consistently and for a long time. Anyone can do this, you just have to keep being exposed to it and muscle memory eventually takes over. This goes for movement and aiming at the same time. Practice makes perfect, there isn't really a magic way to circumvent this. Although I will say mouse and keyboard will always be best to use for fps and rts genre games.
As for the buttons go, you likely will not be able to change the button displays on the screen from Xbox to Playstation without some form of 3rd party software if it even exists. This is mainly because Microsoft owns both Windows and Xbox, has integrated Xbox services within Windows, and also would probably not include a playstation variant, so that they can attempt to sell more Xbox controller. The Playstation exclusive games Sony has been porting to PC via Steam and such might have Playstation buttons displayed instead, but I haven't messed with them on PC before. Steam fully supports Playstation controllers now, and even Switch joy-cons, so there may be some choices in there. I tend to just play the exclusives and third person shooters on console, and everything else on PC.