I have absolutely no idea how or why, but this issue has just suddenly gone away by itself. Pfsense is now able to connect to its repositories yet I have been on shift since making this first post and have not amended any settings. It can't be that the repositories themselves were down, or anything such as that, as I was able to connect to them originally, but only if my NAT rules were set a certain way. I now have both connectivity from pfsense and from all devices on the network, but I didn't do anything. Very strange, has me even more puzzled now!