For your first question, let me review your reasoning. You're observing that if we start out with
El es maestro.
and we modify maestro with an adjective, e.g. excelente, then we need to add an indefinite article:
El es un maestro excelente.
You'd like to know if we need to do the same thing with the plural version. In other words, if we add an adjective to
Ellos son maestros.
must we then say the following?
Ellos son unos maestros excelentes.
Or can we say the following?
Ellos son maestros excelentes.
The answer is, "Ellos son maestros excelentes" is fine.
For your second question, I think you're asking whether it's okay to say the following?
El es el maestro excelente
The answer is, Yes, you can say this, but it's a bit unusual. It means, as Mike said, "He is the excellent teacher." Here's a possible context. For example, you've been telling your brother about an incredible teacher you have, and then you run into him in the grocery store. You might tell your brother, "He's the excellent teacher (I was telling you about)."
Note that "Es un maestro" is also possible, although it has a special meaning: "He's an expert / a genius" or "He's phenomenal!" (Thanks to @Gustavson for suggesting this addition to my answer.)