You want coherent sheaves to have finite global resolutions by locally free sheaves. So definitely you need the regularity of $X$ to ensure that a locally free resolution stops at a finite stage. You also need a global condition such as quasiprojectivity over an affine base to guarantee that you can start the process. (The last condition is not optimal.) Edit: In reading the follow up comments, I realize my answer was a bit cryptic. The inverse map $K_0(X)\to K^0(X)$ would send the class of a coherent sheaf to the alternating sum of the classes in a resolution. In general, these groups behave quite differently. $K^0(X)$ is contravariant like cohomology and $K_0(X)$ is covariant for proper maps like (Borel-Moore) homology. That they coincide for regular schemes is reminiscent of Poincaré duality.