Organisation. And sleep.
Everybody I know who looks like that goes to bed early, their houses are clean and well organised, their clothes are ironed, put away and easily accessible and they wake up relatively easily.
If they've got a full requirement of sleep, so get up with plenty of time, go for a shower in a clean and tidy bathroom, come back to a clean and tidy bedroom, find their clothes easily, have time to sit down and do their hair and makeup, put the wet towels up to dry/into the washing machine, etc, it's easier for them to look calm and polished.
In the evenings, their kitchens are easy to work in, it's simple to whisk around after cooking dinner, they can have a bath/use products to deal with skin or hair issues, they're calm and then waft off to a neat and tidy bedroom (and a great mattress) to sleep the slumber of a relatively carefree existence, ready for the next day of looking marvellous.
Compare and contrast to barely scraping four hours of sleep, waking up three times due to pain or a lump on the mattress/a pillow that just isn't quite right, whatever you do, hauling your half dead carcass out twenty minutes after you should have got up, rummaging in a heap for clothes that don't look quite as shit/haven't got stains or holes, tripping over crap in the landing on the way to a shower where it's hit and miss as to whether it's got warm water or is colder than the stuff in the fridge, you can't find a clean towel, you're cold, running late and all you really want to do is get back under the covers and sleep for a month...well, it's bloody hard to look like a porcelain swan, then.