Generally speaking, the higher the numerical value given to a basestock means the better. Group III is inferior to PAO as PAO's are inferior to Grp V esters. But it's not that simple. PAO/Esters both have qualities each doesn't have which is why we've seen blended basestocks using PAO's + Esters + AN's. For example, Mobil 1, Amsoil or Redline. Redline uses a much higher concentration of Polyolester basestock then M1 or Amsoil.
But realize, you can take a Grp II or III based oil and formulate very well using good additives and chemistry that will exceed a poorly formulated PAO oil. Examples of these would be Chevron Supreme, Schaeffer's and many others.
For longer drain intervals, I have no doubts that PAO's are superior to most Group III's. This is why Amsoil/Mobil use them.