I have a question about the following proof of existence of a model of non-standard arithmetic (taken from wikipedia):
The existence of non-standard models of arithmetic can be demonstrated by an application of the compactness theorem. To do this, a set of axioms $P^*$ is defined in a language including the language of Peano arithmetic together with a new constant symbol $x$. The axioms consist of the axioms of Peano arithmetic $P$ together with another infinite set of axioms: for each numeral $n$, the axiom $x > n$ is included. Any finite subset of these axioms is satisfied by a model that is the standard model of arithmetic plus the constant $x$ interpreted as some number larger than any numeral mentioned in the finite subset of $P^*$. Thus by the compactness theorem there is a model satisfying all the axioms $P^*$.
Since any model of $P^*$ is a model of $P$ (since a model of a set of axioms is obviously also a model of any subset of that set of axioms), we have that our extended model is also a model of the Peano axioms. The element of this model corresponding to $x$ cannot be a standard number, because as indicated it is larger than any standard number.
Why is it acceptable to augment the structure by a new constant symbol $x$?
There's nothing mysterious or underhand going on here. Though there is an important point in the background, which is simply this:
Formally, only stuff on the construction tree of a closed wff feeds into determining the semantic evaluation of the wff.
Now, why is this observation relevant to the compactness argument you are worrying about?
So now to apply this general observation. If there is a model for the axioms of Peano Arithmetic Plus Some Extra Sentences in Whatever Vocabulary You Fancy then the same model cut down to deal with just the original language of PA will also be a model for the axioms of Peano Arithmetic. That's why is perfectly legitimate tactic to establish that there are non-standard models of Peano Arithmetic by cutting down models of Peano Arithmetic Plus ... (Though as @Mikhail Katz points out in his answer, this route to non-standard models perhaps doesn't give you a "feel" for what the models are like.)