Hi ForMyThunder!
The standard n-simplex has vertices (1,0,0,...,0),(0,1,0,...,0),...,(0,0,0,...,1). Now, given a map \sigma:\Delta^n\rightarrow X of our Delta-complex, then we can call
\sigma (1,0,0,...,0),~\sigma (0,1,0,...,0),...,\sigma (0,0,0,...,1)
are the vertices of these maps. A simplicial complex is such that no two maps \sigma_\alpha and \beta have the same set of vertices!
For example, consider the square [0,1]x[0,1]. Then the points (0,0),(1,0) and (0,1) form a triangle which is homeomorphic to \Delta^2, so take that as a first map. The points (1,0),(0,1) and (1,1) also determine a map. Continuing further gives us a simplicial complex, because every collection of points belongs to at most 1 map.
However, if we would take another map from \Delta^2 to the triangle (0,0), (1,0), (0,1) and adjoing it to our complex, then there would be two maps with vertices (0,0), (1,0) and (0,1). This would not form a simplicial complex.
Hope that helped!