Both moveorders are playable and in 99% of the cases the same mainline is achieved. Nevertheless there are a couple of nuances.
1. e4, e5 2. Nf3, Nc6 3. Bb5, a6 4. Ba4, Nf6 5. 0-0,
A) 5.., b5 6. Bb3, Be7 7. d4 (At my opinion the major sideline and this has been played by numerous grandmasters i.s.o. the normal 7. Re1) and now
7..., d6 (7..., ed4: is risky due to 8. e5 while on 7.., Nd4: there can follow 8. Bf7+
8. c3, 0-0 (Bg4!?) 9. h3 (If white wants something else then he should try Re1 or Nbd2) Black has now to choose which mainline he wants to play. It is very likely that white will return to standard theory with 10. Re1 because 10. d5 or other moves are less critical.
B) 5..., Be7 6. Bc6: (Many experts consider this exchange as less critical than the mainline with 6. Re1 so an infinite small error. This doesn't mean that play is that easy for black but in general if black knows some critical lines by heart then he shouldn't suffer that much.)
One example from my own practice...
[Event "EU/M/1234"]
[Site "?"]
[Date "2000.??.??"]
[Round "?"]
[White "Anderson, John"]
[Black "Brabo"]
[Result "0-1"]
[ECO "C85"]
[PlyCount "84"]
[EventDate "2000.??.??"]
[SourceDate "2001.12.02"]
1. e4 e5 2. Nf3 Nc6 3. Bb5 a6 4. Ba4 Nf6 5. O-O Be7 6. Bxc6 dxc6 7. Nc3 Bg4 8.
h3 Bh5 9. g4 Bg6 10. Nxe5 Nxe4 11. Re1 Nxc3 12. bxc3 O-O 13. Rb1 Bd6 14. Rxb7
Qh4 15. d3 f5 16. Bf4 fxg4 17. Bg3 Qxh3 18. Qxg4 Qxg4 19. Nxg4 Rf5 20. Ne5 Re8
21. d4 Bf7 22. a4 Bd5 23. Reb1 Rh5 24. Kf1 Rh1+ 25. Ke2 Rxb1 26. Rxb1 c5 27.
Kd3 h5 28. f4 c4+ 29. Kd2 Be7 30. Re1 Bd8 31. Bh2 g5 32. fxg5 Bxg5+ 33. Ke2 Re7
34. Rg1 Rg7 35. Nf3 Bd8 36. Rxg7+ Kxg7 37. Ne5 Kf6 38. Nd7+ Kf5 39. a5 c6 40.
Nc5 Bxa5 41. Nxa6 Bxc3 42. Be5 Be4 0-1
So what is best? I think it is more a matter of psychology and part of a preparation than a real problem. On both moveorders I choose with white for the most natural mainline with Re1 although for rapid and speed chess I sometimes change to see if my opponent knows the little sidevariations too.