You definitely can paint your refrigerator you just need to prepare the surface first. Maybe some light sand paper (not rough because you don't want to roughen up the surface permanently), then prime it and paint it.
I would recommend taking off the door handles first and wouldn't paint it with a paint brush.
One really cool thing I've seen on line is to paint it with chalk board paint so that you can write all over it. I think it's what the refrigerator is like on Good Luck Charlie on Disney Channel.
