Well, that was a shorter reply than I intended. But you should be able to see that the section you linked (14.1.4 Modifiers) is part of 14.1, History Expansion. Those modifiers don't apply to parameter substitution.
For doing replacements with parameter expansion, you can just use the slash modifier. One / replaces the first occurrence, two //s does all of them:
$ value=/dir/subdir/file.csv
$ echo ${value//dir/_G}
/_G/sub_G/file.csv
That's not a zsh-specific feature; ksh and bash have it as well. Zsh likely has a different mechanism to accomplish the same thing, but I've not needed it so am not familiar with it.
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