Push/Pull will get you better performance than just plain push or pull, however the difference wont be that much.
The reason it will make a difference as it increases the Static Pressure of the air going through the rad, which can be likened to how hard it is being pushed. This is pretty important when your talking thick, high FPI (Fins per Inch) radiators but the H100i is neither.
You will see benefits, but dont expect anything dramatic. Might even be worth going with shrouds instead, as that gives you more effective cooling area since the dead spot in airflow behind the fan motor is lessened, rather than just forcing the air through it harder.