I'm looking for a PCI-e s939 mobo for an ATi radeon x1900 xtx and I have no idea which one is best. If I bought a SLi board would I able to put two ATi cards in it at a later date?
No, you need a crossfire certified board. Boards based on the RD580 chipset is very good afaik.
Next, do PCI-e cards use different power connectors rather than those 4 pin molex connectors i've been using on my AGP card?
Yes, they uses a six pin connector like this:
Four- to six pin connectors (pictured above) exists, so no need to worry (it's included with the GPU?).
Primarily I just want a single card solution but perhaps add an additional card at later date. I understand there are masters and slaves? or something like that. If I bought just a slave would it serve me well as a single card solution?
The slave card will serve you just as well. The master card is only necessary when going crossfire, although you must note that it's based on a XT, not a XTX.
I have read the buyers guide but it has made more confused lol.
I'm the author so some input to why would be very much appreciated.
Any advice would be sweet.
CHEERS.