Nintendo has said Daisy was tomboyish, but we've never seen it in games. She just yells a lot.
Luigi is known as a coward. But we've actually seen that in his actions. His mannerisms express his personality, being jumpy, worried and a coward, even in Smash. There's also something unsettling about Luigi, that comes across in his old final smash and his association with the paranormal.
Luigis is probably the best defined personality in the Mario universe, with Bowser and Wario being right behind him. Daisy is not defined as a character at all, most of her characteristics we know from being told them, but she never really acts like them.
I'd argue that the existence of Waluigi really helped nail down Wario's personality. They sort of moved Wario's bitterness and jealousy towards Mario over to Waluigi and let him focus on being a disgusting, greedy slob.