You could try a heat gun to melt it back into place.

If you know the door manufacturer you can order the plastic surround. It is essentially a sandwich frame inside and out. You would reuse your glass.

I would not try the heat gun idea but IMO you need to address the heat issue before painting since any paint will just go the same as the trim is now.

As MYM alluded to, the surrounds can be replaced and that would be your best bet.

I also agree with the thought that the issue that caused this shoudl be addressed as well. I presume that this is a south or west facing door and is covered by a storm door. You'll want to make sure that storm is vented, particulalry during hours of direct sun. There are some other things that can be done with tint etc to help, but typically venting does the trick.

@millworkman thank you. its an old door, but it says stanley. i can reach out… what does it entail to replace it? can i just remove the surround or would i have to remove the whole piece?

8 screws and the entire unit will come out. It is essentially a sandwich frame. It will be caulked (butyl rubber most likely) that will need to be cut away. Screws should be to the inside.

Would suggest that you save up until you can replace.

Pump white caulk under it then clamp a board across to flatten it.