Hey Gareth,
"Rare" is a relative term. I do have a few ideas depending on what you had in mind. There are some great vendors that keep old heirlooms, then some that are on the cutting edge. Both directions would be uncommon.
As far as species go, there are some US growers that have old, valuable, jungle collected stud plants. Check out Miranda Orchids. He gets lots from Brazil. Andy's is great too. Big Leaf Orchids has some uncommon Phal species if that's your thing. Also, some growers collect unusual color forms of species - I like albas.
Another route you can take is international vendors that are active in orchid shows. Many will post their schedule so that you can pre-order the plants. They bring them through customs and just mail them once in the US. Equagenera and Floralia both do this, I'm sure a few larger Asian vendors do as well.
And lastly, once you find your niche you will stumble upon those boutique nurseries here that only do high-end crosses (for high-end prices). By then you'll be more comfortable with buying a whole flask or expensive division.
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