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I've never done it before, but I would go about it like this:
Make your item, from whatever you want but preferably stuff that's fairly strong, not too much foam or thin plasticard, things like metal, wood (non-porous) solid plastic, wire etc.
Once it's made, give it an overcoat of something like watered down wood glue, something that will set rock hard but won't hide all the details.
You then need to coat it some sort of releasing agent, something as simple as cooking oil or beeswax would work? General purpose grease? Nothing too thick, just the finest of coats to get it back out of your mold.
Now, you have to decide how your going to make the mold, think mould lines on models, you need to decide where the two halves of the mould are going to be so that the thing will come out again.
I haven't got any instant brainwaves for what to use to make the mold right now, maybe plaster? You could even make the two halves seperately... pour your plaster into a suitably sized container (one you have two of or can reliably use again) and then using a datum point on at least one edge, press your piece halfway into the plaster. Allow to set and then remove. Do the same for the other side of the piece, it will take some experimenting to get the two halves perfectly aligned. Clamp the two halves together, preferably with some sort of releasing agent again between the two halves and all over the shape of your thing your going to make, then pour in what your making it from. Allow to set, then split!
Have you decided what your going to use to pour in to your finished mould? Lead is pretty easy to work with but it is damn heavy and has obvious health hazards... I guess you could melt down some old white metal models you don't like?
Edited to add:
You could practice by moulding something simple that already has mould lines? Like the old wrecking ball from Ork trukks?
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