If you have symmetric/Hermitian matrix, I recommend you to use EVD-based approach. Just calculate exp() of its eigenvalues and multiply from the left/right on its eigenvectors. In the general case, however, it is really hard to calculate. EVD-based approach is no good because unsymmetric matrices may be non-diagonalizable.
I recommend you to look at
http://citeseerx.ist.psu.edu/viewdoc/do ... 1&type=pdf and
http://www.mathnet.or.kr/mathnet/kms_tex/230.pdf Pade-based method seems good enough and relatively easy to implement. ABLAS unit, especially RMatrixGEMM, may be handy when you'll try to multiply matrices.
P.S. I've added matrix exponentials in my todo list. But I think that it will take somewhere between month or three to implement given another problems I working on now.
UPD: second link should be
http://www.cs.cornell.edu/cv/ResearchPDF/19ways+.pdf