The simplest answer is that this term, which is used not only with PHP but with most existing languages, comes from linear algebra.
In linear algebra, we say that a value is scalar to denote a number or simple value, not an algebraic structure. To talk about the algebraic structures themselves would be kind of to deviate from the subject, so to the curious I’ll just leave a link to the corresponding wiki from Algebraic structure.
In programming, a variable is to scale if it is a number, a string or another type of "primitive" sayings in various languages - which is distinct from a structure with more logic and set of implicit operations as an instance of a class or a array. And yes, I know that strings are deep down arrays characters, but receive special treatment in almost every language.