🤔 I'll echo the need of measurements. Cloth measuring tape, get your measurements and check them with an online sizing chart. I'm not a fan of the goodwill wardrobe. Some things are fine for costuming, but most is going to be "no style". I would suggest surfing a few websites for styles that appeal to you. Once you find your style, you can usually find similar items on cheaper sites like Amazon.
I've always been a fan of the 30s and 40s. Most of my clothing is of the era, with a few things stretching into the 50s. The clean lines and simplicity speaks to me. Classy, clean, and modest. Some of the girls like Victorian, some modern, some punk... it really is as simple as saying "that's pretty". If you like it, you'll have more confidence wearing it, and confidence is the sexiest attire. It's not necessarily what you wear, but how you wear it. If you're only wearing stuff around the house, get crazy and get what you like.
As for lingerie, that's completely personal preference. Cotton is cheap and easy to wash, satin is a bit more spendy and more difficult to launder. I found a rayon blend that feels like satin and washes like cotton. It's the cool nights fabric from Soma, I'm obsessed. The material is extremely durable and feels simply amazing. I got the cool nights blends for my robe and pajamas as well.
I like trying things on in stores more than going online. Fit and feel are important to me. If you're worried about getting clothes in your home town, hit up a larger city in the area... nobody will really know you there and you can get some help with size and accessorizing. You picked a great time of the year if you're nervous, it is almost Halloween. You can play it off as a need for a costume...