The main cast were 3 characters:
- a girl with a spider hairband and possibly purple hair,
- a snarky blonde guy with a green jacket (I think)
- and a regular kid.
The series was set in a magical boarding school and the regular kid was a new admission.
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Could this be Ultimate Book of Spells (2001)? The main characters include Cassandra, a young witch with a distinctive spider headband and blue hair but a purple dress, which is probably what you're recalling. The other characters include Gus (blond hair, green jacket) and a mortal boy, Verne, who serves as the 'everyman' character.
The whole thing is set in a magical school.