This isn't a good idea. For one, when livebearers get breeding, they don't stop. Even seperating the sexes won't work for a good few months as the female can store sperm. Also, they give birth to a lot of fry. If you can't keep all of them, some will have to end up in your LFS or be re-homed and this isn't a good idea with hybrids because it contaminates the gene pool etc. and can cause some serious problems for one or both of the parent species as well as for wild fish and the environment.
Besides that, most livebearers that can easily be hybridised (namely platies/swordtails/variatus platies or endler's/guppies) are already available. Most guppies you see with swordtails and bold marking are endler's hybrids somewhere back in their bloodline. Platies have been 'enhanced' by crossing with swordtails to produce various fancy fin types and so the swords can get some more colors. Variatus have been crossed with platies to get mroe variatus colors. Then there's the various molly species - the mollies you see in your LFS are generaly a mix of poecilia velifera and p. latipinna or p. sphenops.
Rarer livebearer hybrids include things like cossing various wild swordtail species with the 'domestic' (if you like) xiphophorus helleri. This sort of cross should not be made because it means the, rarer, wild species is being contaminated. Furtehrmore, these mixed fish don't look particularly unique.
The less common hybrids are things like mollies X guppies but this takes a lot of time and patience to do. There's also a high mortality rate of fry.
Another hybrid often available and actualy recognised almost as its own species (somewhat like the parrot cichlid), is the 'black beauty' a skiffia francesae X s. multipanctatus cross. These are quite unique looking and your best option if you want an unusual hybrid livebearer. Getting hold of them is a different matter.
To be honest, you are much better off looking for rare but natural species if you want something unique. If you are specificaly looking for livebearers, look into limias, wild swordtails, heterandira species, goodeids or halfbeaks. Watch out though - they aren't all peaceful and some can be quite aggressive or nippy.
If you aren't after livebearers specificaly, things like badis, ctenopomas, wild betta species, killifish, several pardisefish/gourami species, a multitude of cichlids and oddballs, or look into catfish species (especialy cories as they have generaly similar requirements and stay small), would all suit your purpose. Some grow larger than others, some have more specific requirements and some are more difficult to get hold of than others. Regardless, they are a much better choice than trying to breed a common hybrid livebearer.
If you want something reminiscent of livebearers, just as colorful but unique, go for killifish. Research whichever you choose first though as their requirements and appearances range widely.