The guide is just an overview to help potential customers ("users") decide if the Ariane 5 would work for their payload and mission. Nothing to do with Arianespace operating the rocket.
Honestly though, the information isn't all that juicy. What most people would find interesting has been out there for a long time. The hardware in any rocket looks basically the same since Saturn V, and the only remarkable thing about the software is that it's organized.
Is there anything you'd like me to point you to?