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I suggest you start by reading the Pygobject manual that will give you an overview of how using Python with the bindings. There’s also a tutorial that, even if written for GTK3, will give you the basis for writing an application. I also strongly suggesting looking at the source code of other applications to see how they are written.
https://github.com/timlau/adw_pydemo - this one has been the most helpful. If you build/install it in gnome-builder, you can see all the libadwaita interfaces and how they work. this helped me decide with GUI to use for my app (I picked Flap).