I'm the same way, frugal but wanting to look nice and put together. For me, I'm used to shopping thrift. But in the end, what I find is, a year or two later when I'm purging, I always purge the stuff I bought at thrift stores! It seems that if it's cheaper I'll just buy it, when it's not what I would have bought if I had the $ to buy new.
So, what I've discovered for me, is in the long run it's better to have quality, timeless pieces that last, hold up in the wash (no walmart clothes-they always fall apart after 3 washes for me), and that I really like or love. I think knowing what you really like, what your preferences are will help.
For me its wirefree bras (I'm still nursing but I hate underwire). I absolutely hate to wear synthetic fabrics. The only exception is cotton/spandex blends. I need stretch in my jeans or else they are not comfortable. All clothing has to be cotton, breathable and comfortable.
And 1 or 2 quality pairs of shoes beat Payless all the time. My feet are beginning to become arthritic due to a lifetime of wearing flip flops and cheap shoes. I just shelled out some $ for Dansko sandals and I couldn't be happier. I got them in the end of season sale though for 50% off. I tossed all my crappy sandals and only wear these and am more comfortable.
Makeup and facial care I tend to spend more $ on and try to save on other things. I have sensitive skin and the cheap stuff just does not work for me.
Going quality over quantity is a new thing for me, I've always been Miss Cheapskate and bought thrift (not the most flattering colors, fabrics, fit, etc) and cheap (Walmart, payless etc.). My husband has been working on me for years about this, he def. has more quality items but less of them. I am just starting to come around, but I've noticed it does make you value what you do have.