Yeah you're a bit confused. Don't worry, lots of terms thrown around here, and many people do it different ways to get the same results
The picture in your post is actually a casting from a rubber/alginate mother mold. (Whoo more terms to learn)
In basic molding/casting here are the steps
1) Sculpt
this is creating your object via clay or a medium that will allow you to have the details you want on your item to be casted
2) Molding (Creating the Mother Mold)
Usually done with rubber or in an alginate, and depending on the item casted, backed by a plaster case. smaller items do not need the plaster case to hold the shape. if you do your mother mold thick enough, the plaster is not needed.
3) Casting into the mother mold
laying in fiberglass cloth and resin or using pour in plastic (like Smooth on) into the mother mold to cast your final product.
In the video posted, he's using the Smooth on to reinforce the inside, before attempting to work on teh outside of the helmet
What he did, I'm assuming (and from what I"ve seen elsewhere discussed on this board):
1) Pepped his helmet
2) resin the outside of the helmet so that it has a shape, and won't bend, and seal up any holes that so that his Smooth-ON Pour In Plastic will not run out of it.
3) Smooth-on the inside (2-3 layers) to reinforce the inside
4) From there, he will work on the details on the outside of the helmet by adding Rondo/Bondo/More Resin until he get its to a thickness he wants or to smooth out the "blockiness" as happens with pepakura helmets
From there, its detailing, sanding, smoothing and painting.
Here's another one to confuse you:
You can use your pepakura helmet like a "sculpt" to cast and it would be handled the same way, however some additional steps than the basic molding process:
1) Pep your helmet
2) Resin the inside so that it can support the weight of an alginate/rubber mold
3) resin the outside, so that the alginate/rubber mold doesn't damage the paper
4) Brush on your Alginate/Rubber several layers over your helmet. ANd by several layers, Im mean several applications. To a thickness that it will not warp your shape when you remove the pep helmet from your mold
Addendum to 4 - you can also do a 2 part mold for the helmet so that you only have to 1/2 at a time .
5) once your rubber mold is done, remove pep helmet and then use the mold to cast your helmet in the medium you wish (Pour on plastic, fiberglass, etc)