This thread on Technet Forums details the steps needed to get WDS happening.
This is how far I have got down the WDS track. The boot.wim from the Vista DVD that we have self identifies as "Microsoft Windows Longhorn Setup (x86)" which I have left it as. While the image is being added I will turn on my reference PC and let it run the Mini-Setup wizard post RIPREP, the step that I did with it yesterday. After that's finished I will set it up to SysPrep instead for WDS instead of RIS.
WDS has added the image and a capture image has been created from it. That said, I can't actually view the capture image anywhere in WDS. The next step is the SysPrep of my reference PC. Sysprep.exe and setupcl.exe have to be obtained from the Deploy.cab files that come with XP. These are placed into C:\sysprep on the reference PC along with Sysprep.inf which is the same as for RIS. Sysprep is then run with the /reseal and /reboot options.
Once the PC reboots, it needs to be set up for PXE boot. The systems we are using have the Intel D101GGC board which is the ATI Radeon Xpress 200 chipset, the onboard NIC being a Realtek 8139. Although this type of NIC is well known, it is configured quite differently in the BIOS, perhaps this is a function of the ATI chipset as well. Whereas on the Intel chipset, or Compaqs that we also have, all you have to do is make the network card one of the boot devices (any one) and then press F12 during the POST, the D101GGC requires you to enable the boot ROM, and then at bootup you have to press Shift-F10 when the Realtek boot message comes up, in order to configure the boot manager. Tell it to use the Bios order for boot devices (Int19). The difference is with the Intels/Compaqs you just press F12 at POST to PXE and if you don't then it boots the HDD as usual. On the ATI/Realtek system you are having to configure either the BIOS or the boot manager settings and then it always boots to PXE until the option is turned off. There may be a way of configuring it differently but I haven't worked that out yet.
At this juncture I'm leaving WDS alone for a bit, as it's clear I need a lot more time to set it all up and test it out, whereas for this particular PC I need to get it back up and running quickly.