I used PHP on linux with MSSQL on 'doze 2000 on a project last year and it was pretty much problem free. Having used PHP and MySQL before the process was pretty much identical apart from mssql_ in PHP function names rather than mysql_.
The only problem I ran into was that the MSSQL server had various databases running on the same server under difference 'instances'. The only way to get PHP to connect to them was to find out what port number the instance name mapped to and use the port number instead.
PHP Code:
$server = "servername\instancename"; # doesn't work
$server = "servername:4440"; # does work
$c = mssql_connect($server,$user,$pwd);
mssql_select_db($db,$c) or die("Database connection failed");
This may not be an issue to you anyway. I'd suggest going right ahead and post on this forum if you do run into problems!