Of course there is a technical fix for this called Contran I believe which inhibits transmit should another station be transmitting but it costs money to fit and it would only really be effective if the majority of aircraft were so equipped.
I think the problem is a symptom of frequency congestion and the many different sectors one has to work in today's ATC environment.
Perhaps what is just annoying though are those who go rambling on (usually in a non standard way) on an obviously busy frequency. Whilst pleasantries such as Gooday (or even Hello which seems to be used as standard with a certain big airline I shall not mention) may be acceptable during quiet times, it's not standard and takes up valuable air time.
It's always been one of the standard rules to "listen out before transmitting".