I was a confirmed Stepper until I discovered DesktopX.
Litestep is great, don't get me wrong, but I don't like what they have done with the LS Distro thing. It was supposed to make it easier for newbies but I found it a pain in the butt. Also, if you want to become a themer, DX is a lot more fun to create themes for.
If you want to learn about Litestep, you will have to read everything you can about it before you start to use it.
Remember, Litestep is a shell REPLACEMENT, it replaces Explorer.exe, whereas Desktop X is a shell ENHANCER, it sits over the top of Explorer.exe, so you don't have to mess with your system.ini etc.
They are both cool things to use, but I really believe DX is the way forward, and I wish I had discovered it earlier.
I converted my own Litestep themes to DesktopX themes shortly after I discovered it, and they are much nicer to use in DX form.
This is just my opinion, and I'm sure Jafo will be along soon to extoll the virtues of Litestep, and he knows what he is talking about. Whichever you choose to go with, you will find people to help you here. If I can help you with any DX questions I will, but I am no guru.
Have fun.....

If your diving into Litestep as a newbie, I'd recommend you go the route of OTS. That is short for open theme standard. I suggest this for a couple of reasons.

It has become the Litestep theme format best supported by newly released themes (meaning you should be able to download themes tagged as OTS compliant, and plug and play basically).

Although OTS is only a theme format standard (as opposed to a distro), an installer is available for Litestep that will install a current version of litestep configured obviously for OTS. This is usually found linked from the main page of Litestep.net, but lsnet is currently down. I imagine shellfront.org has a link to it as well.

Because it's a format standard rather than a distro, its easy to swap in a new build when they're available (often daily if not weekly).

There's other reasons related to its "open" nature but likely not that interesting to a new ls user.

Hope that gives a little info on OTS. Mind you as already mentioned, with Litestep there is no way around at least a little reading.

As for DesktopX, I have no first hand experience so can't really speak on it, but I hear nothing but good things. You know that it being a Stardock product it will be polished and professional. And with that likely a higher degree of support and info will go with it as well.

My parting shot is that although in thoery you could run the two together, I wouldn't reccomend it;)