§[cpp.incluce]/2:
A preprocessing directive of the form
# include " q-char-sequence " new-line
causes the replacement of that directive by the entire contents of the source file
identified by the specified sequence between the " delimiters. The named source file is
searched for in an implementation-defined manner. If this search is not supported, or if
the search fails, the directive is reprocessed as if it read
# include < h-char-sequence > new-line
with the identical contained sequence (including > characters, if any) from the original directive.
...so yes, if it doesn't find it otherwise, it always re-searches in the standard include directories.