XML Xerces will match your needs. I am using it and i really like it.
In addition to your first edit:
Since your XMl File is very big you have to think of optimizing your parsing process since lot of memory and time can be used for that.
Found an nice small example to get started:
XML Validation with Perl
Another Add:
If you dont want to write simple XML to your Database...it is important that you have an eye on your data, since your validation is outdated after you've written it to the Database in a different form. Be sure that you validate with a good scheme and some extra validators.
Large XML can be tricky sometimes.
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