The 101 focuses partly on general networking knowledge and then also on general F5 product knowledge. There are a few study guides out there that are very helpful in preparing for the exam. No prior experience is needed (but probably recommended).
The books by Steven Iveson and Philip Jönsson were a huge help for me in passing the 101 and later the 201 exams.
The trial edition VE is on quite an old software version. You could obtain a lab license which could run all of the latest versions for about $99 US.