Saint Astraea actually went to the Valley with a number of people. First she had Garl Vinland her lover who is still there with here at the end, the Moonlight Knight Bito who somehow ends up slug food in 5-2 though there is no proof rumor is he was left to die by Vinland because he didn't agree with Astrea's decisions, and lastly the chick whose name escaped me who used the spear Istarelle she was just clubbed to death by giant depraved ones though....
Moving on.
She is where she is because that is the deepest part of the valley, the literal "core" of the corruption. This is believed to be because that cesspool was the dumping ground of aborted babies of the depraved ones. There she tried to cleanse the corruption only to find out that not only was the corruption more powerful than her but she in fact was drawing her power from the same thing that powered the corruptions effecting the valley, that is, the Old One. That is right kids Umbasa does exist, he just happens to be a soul eating demonic entity from another plane of existence. Realizing there was no "god" or Umbasa (literally speaking this is the name of God in Demon's Souls) at least not in any sense she expected she became mildly depressed. Realizing she got her powers from the Old One she knew she needed more power to hope to effect the valley and to do that she had to become more demonic and take on an actual Demon Soul. Now her motives are pure, she is not evil, there is no debate on that. Her actions were flawed though, you can't cure the corruption and she refused to face that reality and by the time she realized this it was too late. If you look closely in game she is literally tied to the ground, tendrils of red crap have grown into and under her skin and she is now a part of the valley and can't leave period. She really was just waiting to die.
Now why do you kill her? Simple. The only way to end all this crap is to put the Old One back to sleep. The only way to do that is to draw him out and make him open the path to where he is. The only reason he would do that is if all the arch demon's gathering souls for him are killed and his food for lack of a better term is cut off. At which point he will summon the most bad ass dude remaining in boletaria which happens to be you. Astraea has become one of these arch demons and is feeding the Old One souls even if she doesn't mean to so you have no choice but to kill her or you will never get the chance to put the Old One back to sleep. It sucks, but she screwed up not you and because a part of the system because she could not bring herself to kill the depraved ones who actually do have to die in order to stop the Old One.
Hope that sheds some light on it.
PS: The three knights of Boletaria Oolan, Alfred, and Metas are all in Boletaria as bosses. Oolan was known as the leader of a vast horde of men, aka Phalanx, Alfred is obviously the Tower Knight, and Metas is the Penetrator. Likewise you fight all three of them in their "soul forms" (aka their real bodies) at the beginning of 1-4. You can also find all their corpses in game, Alfred and Metas are both in 1-3, Oolan apparently died in her ancestral home at 4-1.
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