It's a lot easier to see the 2/3 nature if you imagine that instead of revealing the goat and then asking if you want to switch, Monty said "you've chosen this door that has a 1/3 chance. I'm offering you to switch to choosing both of these two remaining doors, at least one of which definitely has a goat by definition." This is functionally the same offer. It's 2/3 to switch because you're effectively choosing two doors and having Monty automatically grant you the car if it's behind one of them.