Vladimir is a city in Russia.
South/West/East towards Moscow (Москва) (West) and Nizhniy Novgorod (Нижний Новгород), Kazan' (Казань) (East)
There are clearly multiple ways to leave Vladimir, and the way explained down below is not the most obvious one. However it works out, so, to head both west or east (Moscow or Kazan’), take bus 7C direction south to the very last stop. At this point you have to continue walking south, prepare for a walk of approximately 3km.
After 1 km a petrol station will pop up and a road sign which says ‘Москва’, continue walking down south for another 2 km and eventually you’ll see a cloverleaf-junction heading west as east as well. Enter the road by foot and pick a suitable place where cars pass slowly and have space to stop. At this point you can start hitch-hiking. If you’re too lazy to walk for 3 km, you can try to stop a car right after the last bus stop. It might be a bit harder to find a car next to the bus-stop so you might want to walk and thumb after passing cars, maybe you'll be lucky!
Note: the road and junction are not known by yandex.ru or google maps. Here is the place pointed out at google maps satellite view.
Places to avoid
Accommodation and Sleep
To find a 24 hour cafeteria with free WIFI go to the ‘city’ center. Find the golden gate in the west and turn your back to it. Walk down the road with all the cafés and after 100/150 meters you’ll find the place on your left hand side. It says something as ‘гамбургер’ (hamburger). There is no coffee nor good food, only crappy junk food and free WIFI 24 hours a day.
Other useful info
If you’re in Vladimir to do some sightseeing you might consider going to Suzdal (Суздаль) too. It’s about 40km to the North. There is a bus running for 52 Rubles and you can take this bus at the train station. It’s fairly hitchhike-able though.