Brasilia is the capital of Brazil and is located in Distrito Federal.
Southwest towards Goiânia
First, you need to make your way to Samambaia which is one of the satellite cities on the eastern side, specifically around BR 060 freeway. If you take a metro from Brasilia city, hop into one that goes to Samambaia Terminus. Once there, look for a road that crosses in front of you and is adjacent to the station. You'll need to walk in a south direction to the freeway for about 5-10 minutes. Then you can try getting a ride by walking along the freeway (BR060), or, alternatively, you can find a "Texaco" petrol station on the outskirts of Samambaia - it is located further along the freeway, you can get there with a help of a short ride from someone.
Southeast towards Belo Horizonte, Rio de Janeiro & São Paulo
It is advisable to get a bus to Luziania in the state of Goias. When in Luziania, ask a driver to let you off on the road. Along this part of a freeway (BR 040) there are many truck stops and places to get meals/showers, etc. The ones on the southern edge of Luziania are your best bet. It is possible to make your way to From Luziania go to a petrol station on the motorway.
West towards Pirenopolis & Cuiabá
Catch the bus going to Rodoferoviaria,get out on estation after Rodoferoviaria. There u can start hicth-hiking. It's not the ideal place to start,but we havent waited more than 10 minutes. Normally th etrafic in that places is inmense all the time day/night. This road is leading to all satelite cities around Brasilia(Aguas Lindas...),so be carefull,where to get out.