Tomps are the boys to trust for resin moulding supplies.
If you stick to single piece moulds to start with it is easy to cast simple pieces and you will gain experience with the techniques.
I did all my Termagant bases that way. (The bottom half of the Termagant is a base with a snake creature body attached. The top half is half of a standard
GW Termagant model.
I used the Addition Cure RTV Silicone Rubber for the moulds and the Fast Cast resin for the bases.
http://www.tomps.com/shop/-c-1_7_6.html
http://www.tomps.com/shop/polyurethane-fast-cast-resin-p-129.html
The resin was poured directly into the top of the mould which became the bottom of the base.
I didn't need to use a release agent.
The only difficulty was that the resin is mixed by weight not volume, so I used an electronic kitchen scales to make up my batches. I found a scales accurate to +/- 2g was good enough to measure 20g portions of both resin ingredients and they mixed and set well.
The main thing is when mixing the rubber or the resin, mix it thoroughly but slowly, to not introduce air bubbles. If you whisk it up it goes frothy and useless.
The design of your master sculpt is important. You have to avoid severe undercuts and places where the air can get trapped by the resin.
With two piece moulds you can get around those issues.
Here is an article on making two piece moulds with putty. Similar techniques can be used for silicone rubber moulding compund which is more liquid.
http://www.dakkadakka.com/wiki/en/Simple_Two-Piece_Mold_for_Casting_with_Resin