1. In my experience, TPE is hands down the best for this. But in all fairness, my silicone doll was an older model and hard as a rock compared to my TPE. The newer silicone dolls are probably a lot softer.
2. TPE, absolutely. I have two heads for that TPE doll, and the one with the mouth more open is better to kiss. It is also more interesting with a tongue inserted.