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Cats mark their territory with their own smells, and nothing smells more potent than their own eliminations. When you got her she was anxious to claim your house, and probably chose your couch because you're there often and it's soaked up your scent - she was saying this human and this home are both mine.But why doing it in the first place?
And now, that I have washed everything, and laid a puppy pad on the spot that she likes the most, why is she keeping peeing on the very spot?
This morning I saw her playing and then running onto the couch and peeing on the pad.
Twice!
I went through something similar with my cat - I boarded her for months before her owner decided to give her to someone who dumped her outside for a couple months. She lived like your kitty, sleeping outdoors in a trash heap, and was traumatized when I got her back. I'd had her home for a week and one day out of the blue she took a poop on my bed. A few days later she peed on the other side. I know it was her saying, "I live here, this is MY house, I'm not going anywhere and you can't dump me outside again." She stopped using my bed as a toilet after that peeing incident, but that probably had to do with her being familiar with my house - she realized I wasn't going to let her go and started using her box normally again.
With your kitten, your house is completely new to her and she's terrified of being left outside again - this is probably why she peed on the couch the first time. The fact that she keeps peeing on the same spot (and not on anything else in the house) tells me that she's still smelling her pee in your couch - cats have an incredible sense of smell. Are your couch cushions removable? If they are, I'd take the entire cushion to the coin laundry and wash that with vinegar or an enzyme cleaner.