First, with mesh that dense as you have it there, I doubt you may do much in CC.
Mesh/Skin Weights Edit modes in CC are not optimized to work with such a large poly counts.
Lateral partitioning does not really work well either.
Starting with poor selection tool and ending with necessity to still workout stretched and deformed armpit areas after you spend all that time trying to select arms vertices.
Maybe you will have a better luck with it, but I never had.
Bottom line, you have to skin weight in T-Pose for hoodie and with legs moved apart for baggy pants.
The best, is to simulate your cloth in such a pose outside of CC and import into CC for skin weighting.
If you can't import baggy cloth in correct pose then you might get stuck.
Attempting to fix armpits stretching directly in Skin Weights is hard because Smooth Brush is extremely slow. I bet it would not move on your mesh at all.
Smooth Brush in Mesh Edit mode is a lot faster, that's why I would try to fix it in reverse. So try...
Here is a practical example for fixing hoodie in reverse mode, where I fixed the mesh in edit mode and then reskinned.
Still not sure it will work out for you because of your mesh density. You might have to take it to third party apps such as Blender to do the fixing.
Routine for baggy pants is a bit different. It's better be imported with legs slightly apart to begin with...