Starter kits I've seen tend to use fast-curing resin, on the theory that user will just be wanting to bang out a few copies of something in an evening. If you're a beginner actually looking to learn though, IMO you want to use a slow curing resin, as that will be way more forgiving when you're still learning how to pour, how to manage air bubbles, how to position & sprue parts while making the mold, etc.
Don't bother with actual made-for-purpose mold releases unless you're looking to do a manufacturing level number of castings from a single mold. Just talc the inside of the mold before each pour. This will break the surface tension of the liquid resin, helping it to better flow into details without catching air bubbles, and will act as a mold release in its own right. There are actual mold release powders, but you don't need to spring for them unless you're doing professional production-level casting.
I'm not really a fan of spray releases. Their main plus is that they can replenish some of the oils in the rubber that get destroyed by the resin chemistry over the course of casting, thus extending the total life of the mold. However they don't get into crevices as easily as powders, can impart texture to the resin surface if not applied properly, and don't have the flow-aiding benefit of powders. If your priority is getting the most castings possible out of a mold regardless of quality, then use spray, but if your priority is consistent casting quality over the life of the mold, use a powder.