Speakers first. Why? Because the room is the thing you have the least control over so gotta get the speakers and their setup right.
From there, choose an amp capable of driving the speakers to their max, add a good quality source, and voila!
Is there a rational argument for amp first? I suppose if one has a strong preference for a specific amp. A SET comes to mind. If that is your thing then perhaps nothing else will do. Your speaker choices might be more limited but the right ones are still probably out there somewhere. To each their own.