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>How well would the Ralts line fit into human society?In a human society with pokemon, they already do fit in - as pokemon.
Pokemon of other species have reputations as guardians or helpful spirits without direction from trainers, so it's possible they could adopt a guardian role on their own. For one (or a family) to act human would be highly unusual since they have different motivations and needs (e.g. a human thrives off of positive emotions for different reasons than a Kirlia would). Acting human would be as strange to them as a human in a Gallade suit living in the woods and watching over young Ralts.
>What job would each member be best at?Ralts aren't capable of a whole lot until they master basic psychokinesis and teleportation and would need steady teaching. Kirlia are natural performers and maybe fortune tellers. They're also smart enough at this point to be assistants, with instruction.
Gardevoir and Gallade are more powerful and can achieve a lot with pychokinesis or mind-over-body, but while their intelligence affords them autonomy, they'll need specialized training if the job is neither simple nor one they chose for themselves; they are creatures of (and raised with) passion after all.
>Would they enjoy video games as well as us?Mixed results here. Novel visual stimuli could be just as captivating for a short time, but the video game comes from an emotionless machine they can't connect with. Even dramatic RPGs wouldn't feel right to them; for a human parallel, try playing through such a game without sound ir with facial expressions turned off.
Playing video games with friends is a different matter. They'd more than likely want to play cooperative games (in person) rather than purely competetive ones since the emotional feedback from a teammate differs from the feedback of an opponent. That said, there are bound to be some individuals (likely Gallades with a notion of defending one's honor) who crave that competetive spirit.