Oh man there is a ton of information out there on how to do this! It's certainly very possible and so far as I know before dollyhair.com and other vendors were so common donor ponies were the preferred method for re-hairing a pony, as doll hair quality varies, and at one point it was much harder to find nylon hair of the same quality used by Hasbro.
The metal clamp on an MLP tail can be removed with pliers, there's information on it here:
http://www.aikarin.com/mlp/customs/rerooting.html Ideally you need to be working with a non-rusty tail, or a tail where the rust is very minor and can be washed out. Just be careful, it can be fiddly to remove. I know some customizes even when restoring prefer to remove them anyway and replace them with plastic zip-ties to prevent future tail rust. Others might have more spesific advice.
Hot water will absolutely not harm the nylon that real MLP hair is made out of (assuming we're talking the normal kinds of hair, this does exclude perfume puff hair and sun-changing hair which has a different quality). Bring water to a boil, remove it from the heat, then pour it over the hair, combing it, allowing it to dty straight, and repeating as necessary until it reaches the desired straightness. There's GREAT information here on pony hair restoration, including hair straightening:
http://www.mlppreservationproject.com/hair.html (The whole site is worth a browse if you're into restoration, and has a lot of answers to your questions). Hot water does not affect styling the hair as all it is essentially doing is softening the fibers and causing them to relax. I am assuming the donor ponies have good quality tails to donate, as sometimes when the fibers have become repeatedly tangled, snarled, stretched, and frizzy, getting them back straight can be a real chore.
Once you have the old tail prepped, all it will take is re-hairing as normal.
Edited to add: You probably won't need to worry about getting that 'crimp' in the tail perfectly straight either, as that should be where you'll be tying the knot for your hair weft for the mane. The tail length you're working with will be far longer than the mane you need. In fact, it should give you a good guide to tie your weft!