The answer to your first question is yes.
The answer to your second question, however, is no: in order to conclude that some sequence $D$ is not on your list of sequences $S_1 S_2, . . . $, you need to argue:
For each $i$, $D$ disagrees with the $i$th sequence somewhere: that is, for some $n$, $S_i(n)\not=D(n)$.
(This is just because this is what it means for two sequences to be different! Two sequences are different iff they disagree somewhere; so if I want to conclude that $D\not=S_i$ for any $i$, I have to argue that - for each $i$ - there is some "point of disagreement".)
The diagonal argument picks $n=i$: the $i$th bit of $D$ is different from the $i$th bit of $S_i$, for each $i$. We could pick differently: e.g. make the $i+17$th bit of $D$ different from the $i+17$th bit of $S_i$.
By contrast, what you've described - making the $i$th bit of $D$ different from the $1$st bit of $S_i$ - isn't enough! There's no reason to believe that this actually produces a sequence not on the list.
For a concrete example of how this can go wrong, suppose your list looks like:
$S_1=0111111111...$
$S_2=1000000000...$
$S_2=1100000000...$
$S_3=1110000000...$
And so on.
Then if we do the "change the first bit" trick you describe, the sequence we'll produce is $$10000000000...,$$ which is on the list as $S_2$.
By contrast, the classically-constructed (anti)diagonal sequence is $$11111111111...,$$ which isn't on the list (we know it can't be $S_i$ since its $i$th bit isn't the $i$th bit of $S_i$). Of course, this sequence is in a sense the "limit" of the list, but that's not relevant - it's not on the list.