There are multiple errors.
First you assume that your chance of getting $5$ or $6$ on the last two rolls is the same as the chance that the greater of two dice rolls will be $5$ or $6.$ This includes cases in which the first roll is a $4$ but the last roll is $5$ or $6.$
If you roll $4$ on roll 2, will you really discard that roll and take roll 3 as your final score? (Expected value $3.5$ on roll 3, with a $\frac12$ chance it is worse than the $4$ you got on roll 2 and only $\frac13$ chance that it is better.)
But if you stop after rolling $4$ on roll 2 (as you should), you won't roll a $5$ or $6$ on roll 3.
With optimal play after roll 2 (reroll on $3$ or lower, stay on a $4$ or higher), I figure the chance of getting a $5$ or $6$ on the last two rolls is just
$\frac13 + \frac12\cdot\frac13 = \frac12 < \frac59.$
(You have a $\frac13$ chance to roll $5$ or $6$ on roll 2, and a
$\frac12\cdot\frac13 = \frac16$ chance to roll less than $4$ on roll 2, reroll, and roll $5$ or $6$ on roll 3.)
But also consider that the chance of getting a score of $6$ on the last two rolls is only $\frac14$ (the same as getting a score of $5$).
That's also the chance of getting a score of $4.$
and there is another $\frac14$ probability to end up with a score less than $4.$
So if your first roll is a $5$ and you decide to continue (and therefore discard that roll), you have only $\frac14$ probability to get a score higher than if you stop now, whereas you have a $\frac12$ probability to get a worse score.
Moreover, the possible gain (if you improve) is at most one point, whereas the loss (if you do worse) is at least one point and very likely more.
In problems like this I don't see any substitute for actually working out what the ideal strategy is at each step using actual expected values, which means working backward (is in jgon's perfectly good answer) and doing the fully detailed probability calculations (not just rough lower bounds).