It really looks like an array of dicts would be a better solution here:
var inv_data = [{"Item": "10009", "Stack": 1}]
print (inv_data[0])
inv_data.append("Item": "10010", "Stack": 1})
print (inv_data[1])
But if you really want to use a dict of dicts, you could do it like this:
var inv_data = {0: {"Item": "10009", "Stack": 1}}
print (inv_data[0])
inv_data[inv_data.size()] = {"Item": "10010", "Stack": 1}
print (inv_data[1])