They both need to be the same Gb, so 2x2Gb or 2x4Gb. You used to be able to mix RAM sizes but support for this stopped. Also 2x2Gb in sli still only operates like a 2Gb card. You can mix different brands though, both cards will run at the speed of the slowest card.
I assume your motherboard and PSU are good enough and support sli cards?
Unless you already have the cards I would say this is a waste of time and money. Sli really only makes sense if there is no single card on the market strong enough for your needs. Sell what you have and add any money you were going to invest in a second card and buy a single stronger card to avoid all the downsides of sli which include many games don't support it.