That skirt would be quite straightforward - if you bought a basic skirt pattern, it wouldn't be much different to that.
I am not an expert sewer by any means, but with some MN encouragement I'm making progress. I began with this pattern which you could buy online. The skirt is basically the same as the one you showed, with a ruffle at the bottom instead of the contrasting strip (slightly more complicated to put a ruffle on but not much) and the waistband isn't made from a separate fabric, but otherwise pretty much the same. I'm about to brave the blouse, but that involves buttonholes, which I haven't yet tried. I've also made a couple of pairs of trousers from the pattern, and have made a couple of sundresses from a Simplicity pattern which I can't see on that site.
I can see a pattern isn't necessary for some things, and the advantage of the skirt you linked to is that you can get used to seam allowances, your machine etc without worrying about all the technical pattern stuff, so starting with that would be a good idea. But I do think patterns are useful if you want to make anything even vaguely complicated, and starting with a simple one is a good way to get over teh fear factor. I bought a copy of Sewing For Dummies and referred to it constantly when I was sewing my first skirt - it was very useful.
Top sewing rules (my rules, anyway) - read all the instructions before you start, and if you make a mistake, don't worry - just unpick it and try again. I've been really surprised at how un-home-made everything I've produced looks, and until a couple of months ago I'd only had a couple of encounters with a sewing machine.