You can! Though I'm not sure if PlayTo works, as I don't own a PS3.. But what I did on my old Surface RT on my dads PS3, was to enable media sharing.. and you can then browse your video collection on the surface from your PS3!
What you do is go to computer administration > Services and programs > services... there you have to find the service called Server, enable it and make it start up with the computer! Then you will have home network and network sharing enabled just like on Windows 8!
Hope this helps!