With the following I present a proof to show that it can be done and
perhaps inspire additional efforts at further simplification. A
combinatorial proof would be quite nice.
We seek to verify the identity
$$\sum_{k=1}^n {2n-2k\choose n-k}
\frac{H_{2k} - 2H_k}{2n-2k-1} {2k\choose k}
= \frac{1}{n} \left[4^n - 3 {2n-1\choose n}\right].$$
Preliminary. We get for the first piece in $H_{2k}$ call it $A$
that
$$\sum_{k=1}^n {2n-2k\choose n-k}
\frac{1}{2n-2k-1} {2k\choose k}
[z^{2k}] \frac{1}{1-z} \log\frac{1}{1-z}
\\ = \sum_{k=0}^{n-1} {2k\choose k}
\frac{1}{2k-1} {2n-2k\choose n-k}
[z^{2n-2k}] \frac{1}{1-z} \log\frac{1}{1-z}$$
We may raise $k$ to $n$ because the function in $z$ has no constant
term:
$$[z^{2n}] \frac{1}{1-z} \log\frac{1}{1-z}
\sum_{k=0}^{n} {2k\choose k}
\frac{1}{2k-1} {2n-2k\choose n-k} z^{2k}$$
Now the coefficient extractor enforces the upper limit of the sum and
we get (in fact expansions start at $z^{2k+1}$ which cancels $k=n$
already)
$$[z^{2n}] \frac{1}{1-z} \log\frac{1}{1-z}
\sum_{k\ge 0} {2k\choose k}
\frac{1}{2k-1} {2n-2k\choose n-k} z^{2k}
\\ = - [z^{2n}] \frac{1}{1-z} \log\frac{1}{1-z}
[w^n] \sqrt{1-4wz^2} \frac{1}{\sqrt{1-4w}}.$$
The same method yields for the second piece in $H_k$ call it $B$
$$- [z^{n}] \frac{1}{1-z} \log\frac{1}{1-z}
[w^n] \sqrt{1-4wz} \frac{1}{\sqrt{1-4w}}.$$
First part. Continuing with piece $B$
$$[w^n] \sqrt{1+\frac{4w(1-z)}{1-4w}}
= - [w^n] \sum_{k\ge 0} {2k\choose k} \frac{1}{2k-1}
(-1)^k \frac{w^k (1-z)^k}{(1-4w)^k}
\\ = - \sum_{k=0}^n {2k\choose k} \frac{1}{2k-1}
(-1)^k [w^{n-k}] \frac{(1-z)^k}{(1-4w)^k}
\\ = - 4^n \sum_{k=0}^n {2k\choose k} \frac{1}{2k-1}
(-1)^k (1-z)^k 4^{-k} {n-1\choose k-1}$$
and extracting the coefficient in $[z^n]$
$$4^n \sum_{k=1}^n {2k\choose k} \frac{1}{2k-1}
(-1)^k 4^{-k} {n-1\choose k-1}
[z^n] (1-z)^{k-1} \log\frac{1}{1-z}
\\ = 4^n \sum_{k=1}^n {2k\choose k} \frac{1}{2k-1}
(-1)^k 4^{-k} {n-1\choose k-1}
\sum_{q=0}^{k-1} (-1)^q {k-1\choose q} \frac{1}{n-q}.$$
Now
$${n-1\choose k-1} {k-1\choose q}
= \frac{(n-1)!}{(n-k)!\times q! \times (k-1-q)!}
= {n-1\choose q} {n-1-q\choose k-1-q}$$
Switching the order of the summation,
$$4^n \sum_{q=0}^{n-1} {n-1\choose q}
\frac{(-1)^q}{n-q} \sum_{k=q+1}^n
{n-1-q\choose k-1-q} {2k\choose k}
\frac{1}{2k-1} (-1)^k 4^{-k}
\\ = \frac{4^n}{n} \sum_{q=0}^{n-1} {n\choose q}
(-1)^q \sum_{k=q+1}^n
{n-1-q\choose k-1-q} {2k\choose k}
\frac{1}{2k-1} (-1)^k 4^{-k}
\\ = - \frac{4^n}{n} \sum_{q=0}^{n-1} {n\choose q}
(-1)^q \sum_{k=q+1}^n
{n-1-q\choose k-1-q} [z^k] \sqrt{1+z}.$$
The inner sum is
$$\sum_{k=0}^{n-1-q}
{n-1-q\choose k} [z^{k+q+1}] \sqrt{1+z}
= \sum_{k=0}^{n-1-q}
{n-1-q\choose k} [z^{n-k}] \sqrt{1+z}
\\ = [z^n] \sqrt{1+z}
\sum_{k=0}^{n-1-q} {n-1-q\choose k} z^k
= [z^n] \sqrt{1+z} (1+z)^{n-1-q}.$$
Substitute into the outer sum to get
$$- \frac{4^n}{n} [z^n] \sqrt{1+z}
\sum_{q=0}^{n-1} {n\choose q} (-1)^q (1+z)^{n-1-q}
= - \frac{4^n}{n} [z^n] \frac{1}{\sqrt{1+z}}
(- (-1)^n + z^n)
\\ = - \frac{4^n}{n}
\left(- 4^{-n} {2n\choose n} + 1\right)
= - \frac{4^n}{n} + {2n\choose n} \frac{1}{n}.$$
Second part. Here we may recycle the first segment
from the easy piece $B$ and obtain for piece $A$
$$4^n \sum_{k=1}^n {2k\choose k} \frac{1}{2k-1}
(-1)^k 4^{-k} {n-1\choose k-1}
[z^{2n}] (1-z^2)^{k-1} (1+z) \log\frac{1}{1-z}.$$
The coefficient extractor in $z$ has two parts, the first of which is
$$\sum_{q=0}^{k-1} (-1)^q {k-1\choose q} \frac{1}{2n-2q}$$
which contributes half the value of the piece $B.$
The second is
$$\sum_{q=0}^{k-1} (-1)^q {k-1\choose q} \frac{1}{2n-1-2q}.$$
This yields
$$-4^n [z^n] \sqrt{1+z} \sum_{q=0}^{n-1} {n-1\choose q}
\frac{(-1)^q}{2n-1-2q} (1+z)^{n-1-q}
\\ = -4^n [z^n] \sum_{q=0}^{n-1} {n-1\choose q}
\frac{(-1)^q}{2n-1-2q} (1+z)^{n-1/2-q}
\\ = -4^n \sum_{q=0}^{n-1} {n-1\choose q}
\frac{(-1)^q}{2n-1-2q} (n-1/2-q)^{\underline{n}}/n!.$$
We have for the falling factorial
$$ \prod_{p=0}^{n-1} (n-1/2-q-p)
= \frac{1}{2^n}
\prod_{p=0}^{n-1} (2n-1-2q-2p)
\\ = \frac{1}{2^n}
\prod_{p=-(n-1)}^0 (1-2q-2p)
= \frac{(-1)^n}{2^n}
\prod_{p=q-(n-1)}^{q} (2p-1)
\\ = \frac{(-1)^{n+1}}{2^n}
\frac{(2q-1)!}{2^{q-1} (q-1)!}
\prod_{p=q-(n-1)}^{-1} (2p-1).$$
With $2q-2(n-1)-1 = 2q-2n+1$ this finally becomes
$$\frac{(-1)^{q}}{2^n}
\frac{(2q-1)!}{2^{q-1} (q-1)!}
\frac{(2n-1-2q)!}{2^{n-1-q} (n-1-q)!}
\\ = \frac{(-1)^{q}}{2^{2n-1}}
\frac{(2q)!}{q!}
\frac{(2n-1-2q)!}{(n-1-q)!}.$$
This was for $1\le q\le n-1.$ We get for $q=0$
$$\frac{1}{2^n} \prod_{p=-(n-1)}^0 (1-2p)
= \frac{1}{2^n} \frac{(2n-1)!}{2^{n-1} (n-1)!}$$
and we see that the generic term in four factorials represents this
case correctly as well.
Returning to the sum we obtain
$$-\frac{2}{n}
\sum_{q=0}^{n-1} {2q\choose q}
{2n-2-2q\choose n-1-q}
\\ = -\frac{2}{n} [z^{n-1}]
\frac{1}{\sqrt{1-4z}}
\frac{1}{\sqrt{1-4z}}
= -\frac{2}{n} [z^{n-1}] \frac{1}{1-4z}
= -\frac{2}{n} 4^{n-1} = -\frac{1}{2} \frac{4^n}{n}.$$
Conclusion. We now collect the three pieces
with $A$ first then $B:$
$$-\frac{1}{2} \frac{4^n}{n}
- \frac{1}{2} \frac{4^n}{n}
+ \frac{1}{2} \frac{1}{n} {2n\choose n}
\\ + 2 \frac{4^n}{n} - 2 \frac{1}{n} {2n\choose n}
= \frac{4^n}{n} - \frac{3}{2} \frac{1}{n} {2n\choose n}
= \frac{4^n}{n} - 3 \frac{1}{n} {2n-1\choose n-1}.$$
This is indeed
$$\bbox[5px,border:2px solid #00A000]{
\frac{1}{n}
\left[4^n - 3 {2n-1\choose n}\right].}$$