There is no smithing skill perk for Nightingale Armor set, so at smithing skill = 100, Flawless is the best you can get. You can get it higher by taking up enchanting and wearing Fortify Smithing items. That will take your effective smithing skill to 200, and that will give you Legendary. You can make the armor even tougher by drinking Potion of Fortify Smithing before tempering it.
If you want to make armor even stronger, then you will need to use the Potion of Fortify Restoration exploit.