Fiddler,
For a thumb on a backhoe you could add a completely separate valve, but I believe the most effective would be like RonMar suggested on another thread, either add a spool to the existing stack or put in a diverter valve, so that say an outrigger control would actuate the thumb too. The problem is that if you put another valve in the system to control a thumb you would not be able to use it at the same time as your bucket curl or dipper crowd. If you put the valve before your existing BH valve, then it would have priority and you could not operate the BH controls when you activated the thumb. If it were after the BH valve then there would be no pressure for the thumb when you did anything with the BH.
Mike