Pokémon that can learn spikes
Pokémon that can learn toxic
Pokémon that can learn both by leveling up:
Cloyster, Pineco, Foretress, Qwilfish, Skarmory, Cacnea, Cacturne, Deoxys Defense Form.
By breeding:
Omanyte, Roselia, Snowrunt, Budew, Venipede, Maractus, Dwebble, Trubbish, Ferroseed, Shelmet.
Are you sure you don't mean Spikes and Toxic Spikes?