First of all, usability should always be priority #1 and should drive your design:
However, that doesn't mean your application has to be ugly. And I disagree with those who say "you either have it or you don't." I think almost anyone can develop basic design skills if they put their mind to it. The very fact that you're asking about it proves that you're interested, which is a big step towards learning. And indeed even as a developer it helps to at least have a good sense for what looks good and how to make an engaging user interface. And if it's important you can always hire a professional designer later to take it to the next level.
There are a few fundamental details to design work that have helped me:
1.) Use colors wisely. Dull colors are not bad but they can make the design look boring and uninspired by themselves. If you add exciting, more saturated colors sparingly you can emphasize the more important elements. This will not only improve the look, but it can even be used to improve the usability by bringing attention to elements that you don't want your users to miss. Again, if you overdo this it's kind of like highlighting everything in your physics book. If you do it everywhere, it loses its meaning. I wrote more about colors and contrast in my answer here.
2.) Use white space wisely. This is huge. It doesn't matter if you're talking about a website or a Windows app -- a cluttered application is an ugly one. There is a good article about this relating to web design, but the same basic rules would apply to a desktop app.
3.) Fear not the big fonts. Another means for providing emphasis -- the big font. When combined with proper whitespace, a call-to-action written in great big words can be a powerful thing visually.
Come to think of it, all of these suggestions relate to creating emphasis.