We study the existence of 2-plectic structures on Lie algebras which admit an ad-invariant non-degenerate symmetric bilinear form, frequently called quadratic Lie algebras. It is well-known that every centerless quadratic Lie algebra admits a 2-plectic form but not many quadratic examples with nontrivial center are known. In this paper we give several constructions to obtain large families of 2-plectic quadratic Lie algebras with nontrivial center, many of them among the class of nilpotent Lie algebras. We give some sufficient conditions to assure that certain extensions of 2-plectic quadratic Lie algebras result to be 2-plectic as well. We prove that every quadratic and symplectic Lie algebra with dimension greater than 4 also admits a 2-plectic form. Further, conditions to assure that one may find a 2-plectic which is exact on certain quadratic Lie algebras are also obtained.