You guys aren't defining "better". If you mean "better" as in "faster", then parsing INI files is probably better in that respect, because it doesn't do as much processing. If you're referring to "more flexible" that's a different thing, however. Ease of use is a different aspect too, but it sort of ties in with flexibility. The more flexible you get, the less easy that option may be. For example, regular expressions.
Also, to be effective in parsing XML, wouldnt we need arrays or similar?
errm. We do have something similar. Why are arrays really necessary to parse XML, however? I thought XML was all about the representation of structured data as a universal markup language, not about collections. XML is serialized, there are no arrays. Just elements, nested inside elements. The whole idea of XML is that you're supposed to know the structure of the information.