First of all, you have to understand the way Brazilian buses are routed.
Buses usually go from the airport into the city; not much else leaves from the (any) airport. There are buses that go from the airport to the bus station (rodoviaria) in the (any)city, usually the central point for any further long distance travel.
My advice would be to fly from Vitoria to Rio. I suppose you could also take a bus, but a flight might even be cheaper. Check Azul, Avianca, Webjet, GOL.
From the airport in Rio, get to the rodoviaria Novo Rio.
Costa Verde bus line goes from Rio to Paraty. Scroll down below for a bus schedule:
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