Hi! I don't have any personal experience with character customization in Ren'Py, so I’m not sure. It would probably be hard to make a full customization screen using expressions since you would need to create individual exp files for every single color, outfit, facial feature, etc. you’d like to allow the player to select, which would amount to a lot of files. But, if you want to do something simple like give the player a choice between three outfits, you could totally use expressions!
You might also be able to set up customization by using the Live2D model’s parameters instead of expressions. I know that you can modify a model's individual parameters in Ren’Py using blend_parameter, but I don’t know the specifics, as I’m not a programmer.
If you end up experimenting with it or have any other questions, feel free to reach out!