In this paper we introduce the notion of orbit matrices of Hadamard matrices with respect to their permutation automorphism groups and show that under certain conditions these orbit matrices yield self-orthogonal codes. As a case study, we construct codes from orbit matrices of some Paley type I and Paley type II Hadamard matrices. In addition, we construct four new symmetric (100,45,20) designs which correspond to regular Hadamard matrices, and construct codes from their orbit matrices. The codes constructed include optimal, near-optimal self-orthogonal and self-dual codes, over finite fields and over Z4.