Hi Huw,
I think for big files that aren't regularly updated, SHP is a pretty standard solution, and (with a bit of fiddling) it's perfectly possible to get them into 'web friendly' formats. OS have a lot of their open data in this format and no one's complained so far! I'd definitely stick with WGS84 as a coordinate system though, as 99% of people who do stuff on the web will be using this format.
Hope this helps
Cheers
Stuart
P.S. Out of interest, what GIS system are you using? In my day job at
Lichfield, the GIS officer and I are having a few problems pulling stuff
out of ArcGIS server in WGS84 without there being massive
discrepancies. If you can give us some pointers off-list I'd be eternally grateful!