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The OPF is an epub file that controls how the xhtml files are presented, manifests all of the files in the epub, where metadata about the book is kept etc.
In Sigil, look in BookBrowser and near the end you will see a file not in a folder called content.opf or package.opf or something ending with .opf.
This is typically the OPF file. Double-click it in BookBrowser to make it open in CodeView.
Then launch PageEdit via its Sigil icon (with Sigil showing the OPF in CodeView on top).
Then try working in PageEdit. You should have access to all of the xhtml files and should be able to move among them easily. You should also have access to other images already added in the epub.
If you want to use an image not currently part of the pub, you need to do that in Sigil *BEFORE* launching PageEdit as above.
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