It's probably better to demonstrate this if I set up a microcap simulation circuit: -
I've modelled a lossless transmission line of impedance 50 Ω and length 25 metres. I've chosen this length so that the forward and return pulses do not overlap in time. I've energized the circuit with a 2 volt 50 ns pulse.
If I look at the voltage at node \$V_a\$ I see this: -
So, the initial pulse height at node \$V_a\$ is 1 volt due to the applied pulse of 2 volts being potentially divided by the 50 Ω resistor (R1) and the characteristic impedance of the cable (also 50 Ω).
The reflected voltage pulse has an amplitude of -0.369863 volts and, it is this amplitude relative to the 1 volt originally seen at node \$V_a\$ that represents the reflection coefficient because: -
$$\Gamma = \dfrac{R_2-Z_0}{R_2+Z_0} = \dfrac{23-50}{23+50} = -0.369863$$
Is the reflection coefficient the negative peak of the RED signal
divided by the positive peak of the RED signal
Yes it is but, do yourself a big favour and double-check the model of the RG58 cable you have used. The slopes at the peaks of your pulses are off-putting and, will lead to inaccuracy in how you interpret \$\Gamma\$. Of course, it could be that you need a much better time-resolution for your simulation. For instance, the maximum timestep I used in my microcap simulation was 10 ps; I suspect that if you do the same, your waveform images will be less ambiguous.
Also be aware that if the terminating impedance is higher than 50 Ω there won't be a negative reflection. For instance, we can get the same magnitude of reflection coefficient (0.369863) with a termination resistance of 108.69565 Ω but the returning pulse is positive: -
Another thing to remember is that the ratio of the peaks is only truly representative of \$\Gamma\$ when the source impedance (R1) matches the line impedance.
Lossless line used has L = 250 nH per metre and C = 100 pF per metre and this results in a characteristic impedance of \$\sqrt{\frac{L}{C}}=\sqrt{2500}\$ = 50 Ω.