Koyaanisqatsi, Powaqqatsi - these are usually more considered artsy films but they also small views of different cultures busy at work and how they interact.
Some of the early Nova series programs (early = 1980's) they had some really great stuff such as the Exploratoruim - its history and a really good bit about how they designed/built exhibits (with the founder, Dr. Frank Oppeheimer)... and another one on Open Spaces, particularly centering on the public spaces in New York and the studies of maximizing planning and design for public usability. It just illustrated to me there are a wide variety of real life problems in need of solutions.
Bell Science Educational Series - (1956-64, available on VHS) covers a lot of ground in many aspects of sciences (not just physics and chemistry) Very approachable for a kid from the sticks. :-)
Examples:
http://en.wikipedia.org/wiki/Berlin:_Symphony_of_a_Metropoli...
Minecraft: The Story of Mojang
I would love a documentary that is like M:TSoM, but solely about app developers.
Man on Wire
Most stuff by Herzog
Transcendent Man - Ray Kurzweill
Die Hard (just kidding)
Exit Through the Gift Shop
Ilha Das Flores