As emjay said add it at the end of the boil before chilling, this helps to ensure it's sanitary and lets it dissolve a bit better than adding it directly to the fermenter. In the case of a big beer I'd add both, if your fermentation sticks then add a bit more Energizer.
Nutrient is usually just Nitrogen in the form of DAP, Energizer is Nitrogen and a plethora of other things (Yeast hulls, Magnesium, Vitamin B, Calcium) for the yeast to eat.