Starting “from scratch” as you are is a good place to be. Don’t get intimidated, as you don’t need a lot to look good! With just a couple jackets, a couple shirts and a couple nice pants, you can look good year round without much investment.
If you can afford it, buy the nicest clothing you can find. Well-made clothing will last you a long time if you care for it… although your requirement for stain-and wrinkle-free clothing sounds as if you don’t care for your clothes. Try to find a clothing consignment store if you can, as this is the best place to get well-made clothing at bargain store prices. Even if it takes a long drive to a major metropolitan area, it’ll be worth the trip. I’ve found $1500 jackets for $50 and $250 jeans for $30 at such stores… and often times they weren’t even worn!
At the very least, be sure to wash your clothing in a front-loading machine with cold water and a gentle detergent, dry the clothes as little as possible (don’t dry them if your stains didn’t come out in the wash!), and store them on sturdy hangers in a closet. Warped hangers can warp your clothes over time. We could start an entire thread on clothing care, now that I think about it. It’s easy to care for your clothes with little effort if you know what you are doing.
I’ve been a big fan of sport coats lately. They allow you to look dressed up with naught but a cheap/plain button-up and some nice jeans or khakis. They usually never need ironing, and they can hide the wrinkles and/or stains in your button-up very well! Go for patternless jackets in muted colors (I have a black, a dark grey and a light grey jacket), and they’ll match with most any shirt/pant combination you can pick.
Just a pet peeve of mine: FOR CHRIST’S SAKE TUCK IN YOUR SHIRT! Most button-ups have “tails” for a reason… so they stay in your pants! If you’re going to make the effort to look good, go all the way. An un-tucked shirt looks slovenly IMO, unless it is designed to be worn as such. These shirts will have a level hem in front and back… they’re pretty easy to spot.
While you’re shopping, find a couple nice close-fitting graphic tees. You can substitute these for your button-ups when you want to “dress down” and you can still look very sharp.
As to “nice jeans”, this is a narrow definition IMO. In order to get away with jeans in a business envrionment, they mustn’t be torn, faded or stained in any way. They absolutely must fit you without any bulges or bagginess… this takes some hunting, but you’ll only need one or two pair to last you a while. Ideally, they’ll be as dark as possible, even grey or black.
Complete the look with a nice pair of dress shoes (even slip-ons can look sharp) and you’ll get compliments everywhere you go. It’s amazing how little it takes to look good!
Good luck, young Jedi.