For the most part, you don't. Your sovereign and champs will start with certain spellcasting affinities, according to the different shard types: fire, water, life, death, air, earth. As you level up you will be given the opportunity to upgrade your spellcaster's skill at casting those affinities. Each time you select, for example, a fire magic trait, you'll get access to more fire spells. You can't pick up spells from a school you don't have an affinity for to start with. So, if you find a champ that has no affinities whatsoever, they will never be able learn them.