Zambo,
You are correct that when keeping the w/c ratio constant, the levels of hydration of the cement would remain the same given identical curing conditions.
However, for example if you used a 0.52 w/c mix with 31 gallons/yd^3(497 lbs cementitious), and another mix of 35 gallons/yd^3(561 lbs cementitious), and we assume complete hydration with proper curing consumes or ties up water equivalent to a .38 w/c ratio. The 31 gallon/yd^3 mix will lose approximately 8.34 gallons/yd^3 with complete drying. The 35 gallon/yd^3 mix will lose about 9.42 gallons/yd^3 with complete drying. Higher loss of volume = greater shrinkage.
Bottom line, the higher the paste volume, the higher the shrinkage. The first thing we do when shrinkage is most critical is try to reduce the paste volume through well graded aggregates, aggregate selection, SCM's (fly ash) and admixture packages.
Greg