I asked a similar question a few days ago here: http://news.ycombinator.com/item?id=3007945 (there are some gems in this thread!). I'm actually on the quest to find out what's the best method to learn programming for non-technical people, but I'm still compiling some learnings.

If you're using Ruby on Rails in your startup, start directly with www.railstutorial.org - it's a great introduction to not only programming but all the side things that programmers do (version control, deployment, etc.)

If you need a Python or Ruby introduction, Zed Shaw's are very good too! http://learncodethehardway.org/