More pixels is always better. In this case, I say you want as big a file as you can handle, because when you shoot green screen and want to cut to a closeup from a wide shot, it is nice to have the replacement footage be big enough that you can zoom it in a little without creating visible pixelization.
This sells the viewer that the background is real, because the subconscious expects to see a shift in the width/size of the background when you cut to a closeup. Chromakey backdrops that remain at one size, while the talent in the shots changes, are a dead give-away.
The larger image also allows for control in x and y of the relative positions for best composition.
As to how big to make a green screen backdrop, you really only need it to be very slightly wider and taller than the subject you want to show: the rest you remove in post with mattes and garbage masking.
Don’t forget to make a green floor if you want real full-body shots.