Thanks in advance for any replies! (I have to say reading through the responses across the forum its nice to see such a supportive and welcoming community to people who are coming into the world of Pi fresh faced)
Well. After a few days hunting around and seeing people referring to set the Jump to Letter during controller configuration on Emulation Station I removed and recreated the es_input.cfg file. It prompted me as I configured the device to set a Jump to Letter button and its all working.
Turned out to be a simple issue, as I imagined it would be.