The chemicals have a certain capacity in terms of rolls developed per litre of chemicals. If you have two litres, you can do 2x as much; if you use 300mL, that 300mL will be good for 0.3x as much, etc.
Separately from the chemical capacity, you want to minimise the number of times the developer is used in a rotary process because of oxidation; 5 times is probably the most you would ever consider doing.
Yes, keep spare developer in the fridge. It should keep for a couple of months at 2C (the Fuji developer keeps for months in the fridge under butane; Unicolor I don't know). You can keep stabiliser in the bottle in a cupboard, no special storage required. Blix will kill itself in short order (the bleach eats the fixer), so try to mix up exactly as much as you need, immediately before use. This might mean you need to stockpile a few films and process them in a batch. If you can buy a proper C41 kit (like the Fuji) with separate bleach and fixer (not blix), it will keep much longer on the shelf.
If you see people talking about capacities of 20+ rolls/litre, they're probably talking about the Rollei kit, which is NOT the same as the Unicolor kit.