I have a DB that has a ton of different values mostly stored in one table several tables, all with a structure like:

encounterID | code | Value
1 | 1 | blue
1 | 2 | blonde
1 | 3 | six feet

1 | 99 | red
1 | 100 | 4-door

that might come from a DriverEncounter, which has a DriverEncounter.Person and DriverEncounter.Car.

Is hibernate meant to be used when dealing with dbs of this type? I am totally new to hibernate and have read the tutorials. However, I haven't seen any examples using this type of db. I know it can be used in this case, as I know of people using hibernate that have this type of structure. However, is this considered a good use / best practice of the circumstances in which hibernate is very helpful?

from my experience (N)Hibernate is best used with a normalized relational database. Beware that not all legacy databases are normalized or even relational! These databases are the most difficult to map.
Regarding to your sample I would try to map it in an object hierarchy, using the code as a discriminator value as it looks like each row has a different meaning based on the value of that code.

cheers,
Radu