Older video cards back in the days of the 8800 dident get the same scaling in SLI as modern ones do. I remember hearing a number around 30% increased performance some time in 2007 / 2008 ( around the time of the 8800).
A new card would be a much better fit.
Also, take the one single sledge hammer card advice with a grain of salt. Read some reviews on something like a pair of 6850's. The scaling these days is a lot better ( 1.9-2X in supported games ). So for a game that supports multi GPU you can get the performance of a 580 for half the cost. Thats perf/$ that even a fanboi of big thumper cards like myself cant ignore.
( Note, the XFX 6850's are on sale here in canada again now for 125$ from Ncix.com )
Also DT is not completely true, if the second PCI slot is only 4x or 8x, that limits the maximum bandwidth that card has access too. If your only grabbing medium range cards, they dont even use a full 8x. Some of the reviews I've read have done tests with a pair of 6850's, turning the PCI's from 16x16x to 8x8x and performance decreased by 5-10%.
If your going to go and ram some extremely powerfull cards in there and game on tripple monitors with 120FPS, then yes you definitely want the extra PCI lanes.
Here's a good test to do so you know the bottle neck.
Get GPU-Z and open your task browser, now open a game like RO2 and play for a bit. Make sure that GPU-Z in the background is on its sensors page and is set to update while in the background. Alt tab the game and see how high your GPU usage is and how high your CPU usage is.
It may be likely that your CPU is not powerfull enough to feed your card draw info, this will be apparent if the video useage is not 100% and the cpu usage is. If that happens to be the case then you would be better off upgrading the CPU. There are lots of socket 775 quadcores to be had on ebay now, and a good Q6600 will run you 75$, if your motherboard can handle OC'ing then you can clock that up to 3.3GHZ easily.
It would be better though to go with a completely new rig. Depending on your budget base it around a i5 2500K, or If you'r on a budget, look around for a socket AM3+ mobo with core unlocking, then get yourself a Phenom dual core, the mobo will be able to unlock the two unused cores giving you the equivalent of a Phenom 2 x4 965 ( ~110 $ cpu ).
edit: also get CPU-z , run it, go to the mainboard section, and tell us exactly what kind of Motherboard it says you have.