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Assiming the bike is properly fitted, slacker headtube angle and longer chainstays is the key to comfort on longer rides. If you're doing distance twitchy instant handling isn't welcome, and longer chainstays helps driveline angles and permits wider gearing combos.
I'd scour e-bay over the winter for a Ti frame. Alu would be the last choice based on what you've said, although there are some nice Alu bikes out there. If you can find a cheaper Campy grouppo - Veloce or Daytona/Centaur that would be my pick...
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