Probably shouldn't do that. Caffeine kills plants.
Wow, makes sense. I never stopped to ask why the plant produced caffeine in the first place.
A lot of Starbucks stores will give you grounds for free for use in your garden. I don't know if they recommend composting first or not. My guess is they don't care.
Used, composted grounds are definitely good. Used grounds add biological material to the soil as well and lots of people have good success with that from what I understand.
Compost your grounds, they're great.