Hi,
Gain is the amplification factor.
5V/V means you get 5V out for every 1V in which means that the gain (Av) is 5.
10000V/V is simply a gain of 10,000 (times).
The amount of gain needed can be calculated by: Uo/Uin
(Where Uo = output voltage needed and Uin = input voltage available).
You probably want Uo=5V, but without knowing the schematic of your circuit, I cannot tell you what gain you need.