With photoshop CS5 there seem to be a
few CUDA accelerated plugins, so if they plan to use any of these in the future then I would lean towards getting an Nvidia card. If this isn't an issue then in normal stuff the openGL acceleration can be provided by a low/medium-end card from either AMD or Nvidia (£100 or less).
Therefore, it is really gaming that would require a spend of over £100 - as this will buy you a more powerful card that can deliver better framerates in games (and allow you to run higher settings). For around £150 the best cards are the GTX 560 and HD 6870. If you go up to £160 then the much better
GTX 560 Ti 1GB is available - which is a really nice deal.
However, the real price sweet-spot at the moment is around £200-250 - as this budget will get you a
HD 6950 2GB for £210,
HD 6970 for £240 or the
GTX 570for £240. If CUDA will come in handy, then the GTX 570 is a nice deal.
To beat the HD 6970 or GTX 570 you really need to spend a bit more than £300 - to buy either a
HD 7950 or
GTX 580 you need to spend £348 at a minimum.
As for the best card available, the current single-GPU king is the HD 7970 - but that is an expensive card.
Nvidia are expected to release a new generation of cards in about a months time, so if they are willing to wait till then, the market might change a fair bit due to increased competition (at least we are hoping it will).
As for a performance difference,
this article shows how the £160 GTX 560 Ti compares to the £350 HD 7950. Usually the performance increase going from the GTX 560 Ti 1GB to the HD 7950 3GB is around 60% - though this varies between games. Also when playing at higher resolutions and in games that demand a lot of video RAM the 7950 with 300% more video RAM will often pull ahead further than 60%.