None of the trainers go above 90, you have to earn the last 10 points in any given skill on your own, then you go back to the master trainer of that skill and they give you a quest to earn the right to buy master spells. Not sure how it works with non-magical skills but I'd assume something similar.
For enchanting to be worth it you really have to level it some and invest in a few perks. If you can find or buy gear that does what you want anyway, it's definitely much easier.
