Monoids form a subset of semigroups. The rules that govern monoids are stricter than those for semigroups, so you'd be forgiven for thinking that it would make sense to start with semigroups, and then build upon that definition to learn about monoids. From a strictly hierarchical perspective, that would make sense, but I think that monoids are more intuitive. When you see the most obvious monoid example, you'll see that they cover operations from everyday life. It's easy to think of examples of monoids, while you have to think harder to find some good semigroup examples. That's the reason I think that you should start with monoids.