Hopefully someone else can comment in the technology side (how to merge the different streams). But a first test you could do is to stream the game and just use CH in the same machine. I suspect, unless your machine is a BEAST that CH or the game will get sluggish. Both CH and video capture need to be real time in the same machine, which I suspect will be too much for most machines.
I have a pretty beastly rig to be fair, so i'm not too fussed on lag.
As far as i can figure, I can record CA in the background while the gameplay takes place and to animate the puppet accurately afterwards. I can add those bits in later problem is - recording both at the same time... :/
this is most perplexing...
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I have not used it, but CA can be used for live streaming Adobe Character Animator Help | Stream a scene live . I suspect you may be able to feed it into OBS studio and use it to merge your game play and CA and stream that out live to Twitch/YouTube etc. There was an Adobe ”Tips and Tricks” episode a while back that talked about people using live streaming of YouTube channels I think it was.
Or as you say, record a long CA session, then use Premier Pro to merge the screen recording with superimposed puppet recording later. (If you do this, turn off the CA “scene” windows while recording - it chews up quite a bit of CPU.)