Short answer:
"Should I interpret the division sign as follows:$\left(\frac{64x^3}{27a^{-3}}\right)^\frac{-2}{3}$"
Yes. That is the correct interpretation.
"Or as I originally interpreted it: $\left[\left(\frac{64x^3}{27}\right)\times a^{-3}\right]^\frac{-2}{3}$"
No. But that was a perfectly reasonable (unfortunately incorrect) interpretation.
Long (and weird) answer:
A statement $A \div B$ implies that we think of $B$ as a single "chunk" and it is conventional that $27a^{-3}$, if it is expressed is a single "thing". Why? Hmmm, it's a good question.
This probably isn't a good answer but I think of it this way: Multiplication takes precedence over addition (that is because we can distribute multiplication over addition: $a(b+c) = (b*c) + (b*c)$) and makes addition, in my mind, a fluid ongoing modification, whereas multiplication is a "gluing" bonding modification. We never consider $a - b + c$ to mean $a - (b+c)$ but always to mean $(a-b) + c$ because there is nothing "permanently bonding" about $b+c$ so that whenever we see $b+c$ we think "wow, that is solid 'chunk'".
Multiplication however "feels" different. It is a bonding. In my intuition, it feels almost "chemical" in nature. Where as $a + b - c + d +f$ seems like a liquid flowing process, $27a^{-3}$ seems like a crystalline little rock pebble.
In a way this is why prime factorization is so critical whereas sums are not. If you want to solve $n + m = 27; n,m \in \mathbb N$ we can just let $n$ be anything from $1$ to $26$ because addition is "fluid" and we can break it anywhere. But if you want so solve $n*m = 27; n, m \in \mathbb N$ it is far more finicky. Not any old natural number will divide into $27$. You must tap at it until you find a "subparticle" such as $3$ or $9$ and chisel out the rest.
(Lots of rock and liquid metaphors.)
But... obviously, if I got before a math class and tried to teach that way, my students would ... be perplexed. That's not math, that's ... impressionism.
Well, remember the rules. There's some dumb mnemonic about the orders of operation all you young kids are using these days[$*$]. I can never remember it but ... Let multiplication take precedence over the division symbol. Just... obey, and stop asking questions.... I guess.
Anyhow, unfortunately for you $A\div B$ is really ambiguous. Fortunately "serious" mathematicians stop using it precisely for that reason and pretty soon you'll just use fraction notation $\frac AB$ and won't ever have to worry about this again.
[$*$] I was thinking of PE(M/D)(A/S) which WOULD indicate $5\div 2\times 3$ is $(5\div 2)\times 3$ and not $5\div (2\times 3)$. So basically according to that $64x^3 \div 27a^{-3}$ would be $(64x^2*\frac 1{27} a^{-3})$. But the mnemonic is, apparently wrong. I'd modify is as PE(Coeffecient terms)(M/D)(A/S) so that $5\div 2\times 3 = \frac 52\times 3$ whereas $5\div 2a^2$ is $\frac 5{2a^2}$. However what is $5\div ab$? is $ab$ a coefficient term? Hmmm, I think my assumption would be that it is. Or, at least that'd be what I'd assume if I didn't consciously think about it specifically. But it is ambiguous.