A variety is a geometric object that locally looks like the set of points that are the solutions of some polynomial equations. Any given variety gives rise to a sequence of secant varieties indexed by the nonnegative integers. The kth secant variety is the union of all planes spanned by k+1 points on the original variety. Like vector spaces in linear algebra, varieties have an intrinsic dimension. A naive parameter count produces an upper bound on the dimension of the kth secant variety called its expected dimension. A secant variety is called defective if its actual dimension is less than its expected dimension. Despite being well understood in a few interesting cases, the classification of varieties with defective secant varieties in general remains far from complete. For a specific class of varieties called smooth toric varieties, our goal is to determine which ones admit defective secant varieties. Using the computer algebra system Macaulay2, we conducted experiments on this class of varieties and collected data on defectiveness, focusing on varieties of low dimension and Picard rank. Toric varieties have strong connections to combinatorics and convex polytopes; for any toric variety, there is a corresponding polytope that contains data about the variety. From the polytope, we are able to construct a particular kind of matrix that encodes information about the variety and its secants, which allowed us to prove defectivity for various Picard rank 2 toric varieties. Conversely, applying results from a paper by Laface–Massarenti–Rischter (2022) to the polytopes, we were able to prove non-defectivity of all secant varieties of certain toric surfaces with Picard rank 2. These statements together yield a classification of defective secant varieties for a subset of 2-dimensional smooth toric varieties with Picard rank 2.