http://siliconangle.com/blog/2012/03/20/how-an-established-company-can-start-doing-devops/
finding an discrete project that members of both the development and operations teams collaborate on
He suggests that developers who want to get started with DevOps start by reaching out to ops and getting themselves on the call list so they can see what sort of issues ops has to deal with every day. If you're in infrastructure, he suggests reaching out to development and getting in on some build meetings and learn about how that process works and the pressures they are under.
Starting with small, pilot programs and taking small specific steps are a great starting point. Even if a "pure" agile/DevOps methodology can never been adopted at a company, certain proven technologies like configuration management and practices like putting developers on the call rotation can improve productivity and collaboration.