Fan design presumes that on the inlet side of the fan is a volume of air that is available to be pulled through.
When a fan is put in "Pull" configuration, that source of air is constrained by that which has "flowed" through the radiator and you end up with a lower inlet pressure as a result of the inlet to the fan trying to pull air trough the radiator just for the fan to do it's job.
When in push, the EXIT of the fan is slightly obscured by the radiator, but the source of air is not, therefore more air flows...
The hows and whys are widely discussed, but the facts remain measurable and real - push is better - push pull is best because it moves the air away from the obstacle (rad) allowing a greater net flow.
For some experimental data which I think sums it up quite nicely, see
http://www.overclock.net/t/1292456/1-fan-vs-2-chapter-2-push-vs-pull