(3) vs 3 is a both really. In say smalltalk you can call 3 and it would return 3 because semantically it's an object where as in lisp it's not callable (even if in CL it may be represented as a CLOS object I don't know)
syntactical ( ) isn't actually a procedure call we can see this in (define (id x y) (..)) or (let ((x 3)) ...) in the theoretically pure Lisp semantically it's just a leaf in the tree but as part of an if-block in a real language it gets treated as procedure call even if it makes no sense.
The syntax is the same. Both are s-expressions. The difference is how a particular implementation interprets them. In this example, it would depend on the semantics of def.
(case id
(10 (foo))
(20 (foo) (bar))
(otherwise (baz)))
The expressions are written using s-expressions as data. But still there is structure in those s-expressions, described by the EBNF syntax of CASE.
Every special operator and every macro provides syntax. Since users can write macros themselves, everybody can extend the syntax. On top of s-expressions.
That is interesting. I've always considered lisp in terms of denotational semantics. In fact, I wrote a toy lisp in which the complete grammar was basically
list -> ({symbol | number | string | list}*)
and then it was up to the interpreter to decide the meaning of special forms. (I say "basically" because there was also desugaring of '(...) to (quote ...)).