== KDE3 - the (alternative) Desktop Environment ==
one of the most annoying thing when moving from xP to Linux is... the GUIs
Gnome (3) is known for being restrictive (initiated by Canonical, the "company" behind *buntu which is sadely renown for... imposing their views on the users, mostly because they always considered that Linux users are idiots unable to handle... Linux
KDE4... well, if you stayed w/ XP because of vista, you definitely don't want to go down THAT path
its gratuitous effects which bring to its knees even decently powerful PCs...
KDE3? two ways to get this proven UI
-1- is to install Trinity Desktop Environment ( http://www.trinitydesktop.org/ ) a distro independent community lead by Timothy Pearson that maintains the code of KDE3
as the community is independent of KDE.org they are not allowed to use the KDE acronym anymore and thus use TDE instead
installation of TDE can be a little tricky as it is independent of any distro; TDE makes a good effort maintaining repositories for many common distros but are not always available for the latests version of each distro which forces the user to stay w/ an older release; furthermore distro upgrades are often problematic as they require a tight integration of all the repositories which TDE can not provide.
== -2- openSUSE ==
you don't mention it at all thus maybe you already tried it and discarded it?
or maybe you didn't bother?
in either case, the openSUSE community has continued the development of KDE3 (even though openSUSE was a precursor in the KDE4 development) and for each new release / version, the KDE3 repository is updated and available for install as well as upgrade from previous versions (i recently did an upgrade from 11.4 evergreen to 12.3 just by updating all the repository URLs in YaST2 (Yet another Setup Tool - i'll get to that) and hitting the update [all packages] if newer version available
independently of that i also made a new install of openSUSE 13.1 without any other DE (thus KDE4, Gnome or so) then KDE3 and got a "clean" KDE3 install with a minimum of libraries from other DEs
post a specific question if interested
YaST2 - Yet another Setup Tool or... THE setup tool?
i choose openSUSE instead of vista as my primary OS after having been playing around w/ various Linux distributions - at the time, the openSUSE DVD (10.x) was the only one able to start the installation w/out having to tweak the install command line with extra parameters / options ~:o}
admittedly my PC wasn't exactly your run of the mill XP comp ¦-)
the beauty of YaST2 is that the install starts right into it (you can even choose the native resolution of your screen!) and lets you set up the installation in an easy consistent graphical environment.
i have been trying out several other distros (debian or fedora based mostly) in the past few months and YaST2 is really a (distro) setup tool in a class of its own
also for upgrades, as outlined above; for each install / update it has a thorough dependencies check & a nice integrated window offering solutions in case of dependencies conflicts - very nice & unknown from any other distro (with that nice integration WITHOUT COMMAND LINE)
== smoothen transition - VirtualBox ==
instead of "live CDs / DVDs" why not installing VirtualBox on your XP environment and give various distros a run for their "money" in it
of course, the 32 bit of XP limit the amount of VRAM you can assign to a virtual machine, but for the install RAM isn't that critical - and the "tight memory" situation will give you better feel of how ressource hungry the various distro / configs are after setup