Are these tanks planted? There's no point in adding CO2 if you don't have live plants.
How: For a small tank, you could go with either DIY or pressurized CO2. DIY is messy and cheap to start. Pressurized has a high buy-in cost, but it's cheaper in the long run.
When: After you have live plants. CO2 isn't necessary in low-light setups, but it's still beneficial. If you've got a lot of light, you'll need CO2.
Why: Plants are made of a lot of carbon. They need a supply of carbon to grow. CO2 provides the carbon. Plants need a balanced diet. Without the carbon, plants can't use other fertilizers as effectively, which opens the door for opportunistic algae to grow and muck up the tank.