(This is the kind of thread that usually derails from simple CSS question to HTML vs XHTML, so get used to it

)
Regardless of all the issues on HTML vs XHTML you will need to learn how to write markup language (the 'ML' part of X/HTML) before the CSS you learn can be applied to use.
(Btw, X/HTML and/or (X)HTML are common shorthands for HTML/XHTML)
All the html tutorials I seen mainly concentrate and waste time in so much as they focus alot of formating within html and that is something I cannot see myself doing much as I will use css.
Actually, before you know how to format things with CSS, you'll have to learn how to format things within HTML. The reason is that you'll have to learn how things were done in the past, find the alternative using CSS, and then move there. Some of the CSS "codes" are actually derived from the HTML attributes. So, knowing how the HTML attributes control appearances may be helpful. Also, it might be helpful in cases where you find yourself stuck when changing CSS but the formatting stays, as sometimes there might be formatting leftovers in your X/HTML.
(If it's over your head, that's fine. You'll get it eventually

)
As
MegaMan1311 said, CSS is what's used to change the appearance of everything defined by X/HTML. So, without having something to change, you won't be able to experiment with the knowledge you just learned.
The good news is, you can learn X/HTML without having to learn CSS. The bad thing about this (X/HTML only) is, if you were to change the appearance of everything you have built, you'll have to do it the crude way, and end up making your page less efficient.
What's the fastest way to learn X/HTML? Practice, practice, and practice.
I don't know of any video tutorial on this subject (used to learn from geocities and old textbooks), but books might be better because what you need to learn are the syntax and not how to type them.
Start with a simple page. Think of a simple hobby of yours, and build a dedication page for it. Then, start adding things to it and before you know it, you'll be learning more than you initially planned to.
With regards to XHTML vs HTML: I used to start with HTML, then moved on to XHTML and finally went back to HTML 4.01 STRICT. What's more important is actually making sure you use a strict version of either one, stick with it, validate against it, and make sure you follow the guide for either one carefully.
If you feel like reading more about XHTML vs HTML, click
here or
here. Otherwise, skip CSS for now, start learning
HTML or
XHTML (pick one), then go back to CSS.
-stndn.