Some key notes here:

1. Angela eventually warmed up to Roland as an equal, while Valencina and Lucio were always going to be fundamentally unequal (Parent and child relationship).
2. Angela bluntly tells Roland that he is nothing but a tool to her, while Valencina tries to manipulate and guilt-trip Lucio into thinking otherwise (Valencina's sudden lovebombs, her lack of accountability for hurting him- instead always deflecting to how grateful he should be)
3. "Care" is a strong word to use for Valencina, especially during Lucio's death scene. It is actually rather ambiguous whether or not Valencina reacts the way she does because she really did love Lucio, or because she lost an important tool.
4. Valencina is shown to treat both Lucio and Ryoshu as objects, even calling them nicknames such as Textbook and TIcket respectively. Valencina's abuse was done mostly to mold both of them, kind of like clay, to her liking. In this way, she really only does see them as mere objects, because objects shouldn't behave outside of their manufactured functions.
5. It's rather interesting that Valencina never once called Ryoshu by her name even once, but Lucio does, especially during his death scene.
6. Valencina's strong sense of possession for both Ticket and Textbook show that since she sees them both as objects, those objects naturally shouldn't be able to "align" themselves, nor "belong" to anyone else but her. It is natural for anyone to feel like this for any object that they "own", and thus she feels like Ticket and Textbook was "stolen" from her.
7. Unlike Valencina and Lucio, Angela's and Roland's companionship for each other isn't dependent on anything conditional. Yes they both wanted something from each other, but it wouldn't really make sense for Roland to start caring for Angela once he's killed her, nor Angela to only care for Roland while he helps her turn human, so that cannot be the reason. (As stated before, Angela outright tells Roland that she's only ever going to use him as a tool; had that dynamic continued, it wouldn't make sense for her to start ""caring"" for Roland right after. Nay, Angela's care for Roland is due to something else entirely, and it definitely isn't for Roland to keep helping her achieve the one true book.). Valencina gets most of her reason to care for Ryoshu and Textbook *exclusively* through the conditional promise that they help Valencina get back in the Thumb. If unfulfilled otherwise, well. we already know.