Hey Keith,
I can't answer the best place to get supplies in UK, but no doubt someone else can.
As far as H&S goes, this stuff isn't terribly toxic, either the RTV mold rubber or the resin itself. Obviously you don't want to ingest it, and you want to avoid prolonged exposure to your skin, but ventilation that is sufficient for your other modeling tasks should be fine for this as well. You probably want to wear latex gloves and keep a roll of paper towels around to sop up any spills, but really, common sense and a tidy work area to start with should see you fine.
Legos required? Hardly. I like them because you can reuse them and they are modular. Using them makes it very easy to estimate mold volume and thus the amount of material you need to mix. But you can use almost anything to make mold boxes. MDF, styrene sheet, cardboard are some of many options.
One piece molds are super simple to make. Anything that doesn't have any undercuts is a candidate. I have been busy making oil tank caps lately with 1 piece molds.
2 piece molds are a little more complicated, but still easy enough. There are two basic methods that I know of:
1) suspend part in box and pour rubber to separation line. Wait for that to cure, coat with release, and pour 2nd half.
2) embed part in clay up to intended separation line. Pour rubber. Once cured, deconstruct box, remove clay but leave part embedded in RTV. Rebuild box, flip over, and pour 2nd half.
With either method you need to create some kind of registration so that the mold halves line up correctly when you are ready to pour parts. In method 1, the easy way is to carve little pyramids in the 1st half. In method 2, the easy way is to poke dimples into the clay surrounding the part.
Once you have the two halves of you mold, you need to create a pour spout and at least one vent. This is probably the area that you'll spend the most time perfecting. Basically your #1 enemy is bubbles in the resin. Ron and Lucasz etc have degassers and pressure pots that help them control bubbles. You will not

.
I have slowly learned that bubbles like to form in sharp corners as well as in any high pockets in the mold. I've found that a disposable pipette (like I use for mixing airbrush paint) is great for injecting resin into detailed molds. I've also experimented with "painting" resin in the cracks and crevasses before assembling the mold and pouring.
Hope that is of some use. I encourage you to try this, I think you will discover that it is lots of fun, and is kind of liberating in a way, too.
Cheers