This is easy if your matrix is nilpotent or diagonizable.
If it is neither of those, then you will want to triangulate your matrix to write it as a sum of a diagonizable matrix and a nilpotent matrix.
Remember exp(A) is defined as a taylor expansion exponential function, the series actually converge for any matrix A, so in principle we can always express exp(A(t)) in this way, then each entry of exp(A) is an infinite series of numbers, so you can try and work out the sum to get a closed form. There're better ways to find the closed form of exp(A), if A is diagonalizable just diagonlize it, if not you can always use a Jordan decomposition, it works in a similar manner.