I cannot find the MSI format specification. It says that its an open standard, but I don’t see any documentation – just bits and pieces of information here and there.
I want to modify some .msi installer, but I want to understand first what it is doing.
Sounds like you got a misunderstanding of Microsoft’s promise.
The full list of the open specifications can be found at
http://www.microsoft.com/openspecifications/en/us/programs/osp/default.aspx
Since MSI is not listed within, you can safely assume that it is a private standard and won’t be shared to general public.