(disclaimer: I don't consider myself an expert in this)
Are you thinking finite dimensions?
To be honest, I would simply say to all your questions "it is when it is." Though there are some special cases, such as all Hermitian operators being diagonalizable, and any matrix with distinct eigenvalues is diagonalizable as well.
As for having distinct eigenvalues, I can't imagine a simple criterion: I would think you'd just have to calculate it. I can imagine things like "a matrix has distinct eigenvalues iff its characteristic polynomial has no repeated factors", but that's rather trivial.
If you're working with an infinite-dimensional Hilbert space, then all of these issues become much, much stickier, and you have to appeal to things like distributions, or a spectral theorem.
If you dig through the "links" link at the top of this website, you will come to an online book "Physics for mathematicians". It treats the mathematics of elementary QM in a rather rigorous manner, including some technical details that I had never seen elsewhere. (e.g. that most interesting operators aren't even defined on all of your Hilbert space, and that there are Hermetian operators that are not self-adjoint!) I rather liked it.