I saw Led Zep in 1972 at the Balto. Civic Ctr. and they opened with "Immigrant Song". Plant absolutely *nailed* the opening wail, and that is no small feat of you know the song.
I would also have to say that the Who's Roger Daltrey and Free/Bad Co. singer Paul Rodgers were among the best rock singers of all time. Ian Gillian of Deep Purple fame would also have to be in the mix...
As for absolute vocal mastery, I don't think anyone has bested Judas Priest's Rob Halford when it comes to range, power, etc. Listen to their breakout album "Sad Wings of Destiny" to hear a singer that has it all...
-RW-