Two sets are identical if and only if they have exactly the same elements. $\{\emptyset\}\not = \emptyset$ because they don't have the same elements: The first set has a set as an element (namely the empty set), the second one has no elements at all - thus they can't be identical.
More formally, the cardinality (i.e. the number of elements) of $\{\emptyset\}$ is $1$ ($|\{\emptyset\}| = 1$), while the cardinality of $\emptyset$ is $0$ ($|\emptyset| = 0$). If two sets already differ in the number of elements they have, they can not be the same.
To determine the cardinality of a set, it isn't of interest what the elements of the respective set contain (i.e., that $\emptyset$ as an element of $\{\emptyset\}$ contains no further elements), but what the set itself contains - you only need to look at what is immediately inside the outer brackets.
In this case, if you re-write $\emptyset$ as $\{\}$ and $\{\emptyset\}$ as $\{\{\}\}$ and then look at the content of the outmost brackets, you will see that $\{\{\}\}$ contains the element $\{\}$, while $\{\}$ contains nothing at all.
As for your question,
Is it just because the Empty set already refers to there being a set
present and so it is just the same argument that $\{ \{3\} \} \neq \{
3\} $?
yes,that's exactly the reason. With $\emptyset$ being a content of $\{\emptyset\}$, there already is "a set present" (and thus an entity present in the outer set), and this is the same as the fact that a set containing a set (which further contains a number) is not the same as a set containing a number.
It might help you to imagine sets as boxes with stuff in it. So, $\{apple, orange, \{pen\}\}$ would be a box with an apple, an orange, and another smaller box in which there is a pen.
$\{\emptyset\}$ is a box with an empty box inside; when you open the outer box, you will be happy to see that it has something in it - namely a box, and that you might get disappointed about this inner box being empty is irrelevant to the fact that the outer box itself that we are talking about does have something in it, namely a box.
$\emptyset$, on the other hand, is really just an empty box: If you open it, you will find nothing. And an empty box is obviously not the same as a box in which there is a box.
As for the second part of your question:
The union between two sets $X$ and $Y$ is the set of all elements that are in either $X$ or $Y$. More formally, $X \cup Y = \{x : x \in X\text{ or }x \in Y\}$.
This means that you go and "collect" everything from both $X$ and $Y$ and put it together in one set. Now it is clear that this set will contain everything which is in $X$, but if the second set is the empty set, there will be no elements to further add to the union of the two sets. Thus, you will end up with only the contents of set $X$, since $\emptyset$ can not contribute any to it.
This means that unifying any set $X$ with the empty set $\emptyset$ will result in $X$ again; formally, $X \cup \emptyset = X$.
To pick up the box example again, you take a box $X$, pour all its content into a new box, and then additionally pour the content of an empty box into it. Unsurprisingly, your newly created union box will contain exactly what was in box $X$ before.
A similar reasoning applies to the intersection between two sets $X$ and $Y$, which is the set of all elements that are contained both in $X$ and in $Y$, formally $X \cap Y = \{x : x \in X\text{ and }x \in Y\}$. You can informally also word it as "the set of all elements that $X$ and $Y$ share".
What you are more or less doing here is taking out each element of set $X$ and check whether it is also contaned in $Y$ (or vice versa); if so, this element will be part of their intersection, otherwise not. Now which elements does any set $X$ share with the empty set? Not much: Since the latter has no elements at all, the search for any element which is in $\emptyset$ and also in $X$ is of no avail, you will end up with an empty set again.
So for any set $X$, the intersection with the empty set $\emptyset$ will be an empty set, as the two sets share no common elements (because $\emptyset$ has no elements at all); formally, $X \cap \emptyset = \emptyset$.
In terms of boxes, you create a new box in which you put all the things that you have twice, once in box $X$ and once in the empty box. You will be done very quickly: As the second box is empty, there is nothing to put into your box of shared elements, thus, your intersection box will remain empty.