Let me give two examples, however not so elementary,
- The proof of the degeneration of the Hodge-De Rham spectral sequence by Deligne and Illusie in positive characteristic.
The basic assumption in Deligne-Illusie's theorem is the existence of a lift over the Witt vectors $W_2$. Hard to state within varieties. Moreover, Raynaud gives applications to instances of the Kodaira vanishing in positive characteristic.
- Grothendieck's study of the fundamental group.
The notion of an étale morphism can probably be discussed within varieties, but one needs formal schemes, and the invariance of the fundamental group by a nilpotent immersion. But at the end, the result can be stated within varieties!