No!
With SLI or Crossfire, the VRAM does not stack. If you Crossfire two (2) R9 280X with 3GB of VRAM, you still technically have 3GB of VRAM. But since each card is only rendering half of the screen, each card will require less VRAM and allow you to increase your resolution and FPS.
I know this makes NO SENSE what so ever, but Crossfire and SLI, do not stack VRAM.
Before I advise on getting a second R9 280 or a GTX 980 Ti, what are you trying to do? Game in 4K or max out some more settings?