I'll be posting later, I'm currently at my mom's house. Might be able to squeeze one in soon, but if not I will get one in tonight.
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All the Spirit Kings have a physical link between their realm and ours. Spitfire's is in a Volcano, the rocks his skin and the Lava his blood. Being the Fire King's Blood, it can burn anything that comes into contact with it, even other fire, Beings of fire that would otherwise absorb the heat and flame, and creatures immune to conventional fire.
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Technically, the Empyrean that Emily uses is just a replica. Rather good replica, but still not close to the real thing. Only Spitfire can use the actual Fire King's Crown, because it is his, and he doesn't share.
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Is he immune to fire internally as well?
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*Emily casually creates a tongue of Empyrean; The Fire King's Crown on the tip of her finger without saying anything*