Yes, you can uninstall 2012 and then install 2013 first.
As long as you change the path variable, Emacs will find it. The path variable can be found by:
1. right clicking my computer 2. going to properties 3. then advanced system settings 4. and in the systems properties window go to environmental variables Once there, you will see a systems variables box with a scroll bar and this is where you can set and change path variables in Windows.
I don't use Windows so I have not idea what you would change the variable too but that is where you will find it. Also, I am not sure what it will be called but it should be obviously related to TeXLive.