Keep in mind that the geltimes given are just guidelines, and can vary from batch to batch. Also viscosity and rheology can vary.
The times given usually are in 100 gram cups, so a relative large mass. Thin film times are longer.
Also keep in mind that thin vinylester (like in a thin coating) can refuse to cure, even when the right amount of catalyst and initiator are added. But when you do thicker coatings (gelcoat) or laminates you should be OK.
Another thing to watch is that epoxy has a lot slowe cure. It first starts to thicken up, then becomes syrup, then a paste-like consistency, then becomes solid. Vinylester does the same, but the time from slightly thickening up to solid is much shorter. If you want to vacuum bag, if you see the resin thicken up, basicly you are too late. With epoxy you still have time to apply a vacuum bag.
What to do: From your first batch, save a bit in a 100 gram cup and set it apart. As soon as that cures, it is time to bag. (same works for epoxy)
Also make sure your catalyst (peroxide) is of a sufficiently slow type. You can even add a retarder if neccesary.