It's the capital city of the state of Espírito Santo, Brazil. Hitch hiking in the area is beautifully easy, and to reach any bigger place you would generally just follow the road BR 101.
As for food, there are several vegetarian options in the city. Dumpster diving isn't usually the best idea because of the high temperatures, but there is plenty of coconut trees on the beach, as well as dumpster cocos by the agua do coco stalls: they just use the water and throw away the rest, so bon appetit!
It's a good idea to look for a safe and dry place to stay. The weather is usually great, but when it rains, it very often floods the streets and I've seen several drowned cats floating around. CouchSurfing community there is really strong so you won't have any problems with that. They have weekly meetings with lots of people there, so even if you're not lucky finding a host - just go there and see who takes you home.
Vitória is connected with some other cities around and looks pretty complicated on the map, but it's still very easy to hitch out of it. Just try to walk to the road 101 or 262 (it might take around 1-2 hours, depending on the part of the city you're in). If you're lazy, ill or tired, ask for buses going to the border districts, like Marcilio de Noronha or Sao Francisco (going south) or towards the airport (going north). There's a lot of trucks crossing the country in both directions going through there.