Because the overlay is not applied to the nixpkgs instance used by your NixOS config.
You need something like
{ inputs, ... }:
{
nixpkgs.overlays = [ inputs.poetry2nix.overlays.default ];
}
For example, if you want to work this into some existing file like your nixos.nix
:
{ inputs, pkgs, ... }:
{
environment.systemPackages = [
(pkgs.callPackage ./thePythonPackage.nix {})
};
nixpkgs.overlays = [ inputs.poetry2nix.overlays.default ];
}