I'm assuming you want to add values that are Numista generated (on the coin page) and not the Buying price you input when you add a coin.
If I understand correctly, I can't send my valuation request to a moderator or country-expert or whatsoever.
No, that is outside the the duties of the (volunteer) moderators and (volunteer) country experts/referees. You can submit requests for valuation of individual coins on this forum (please read the Forum policy first) but any valuation would not flow into the Numista generated value in the spreadsheet export.
Furthermore, only if other collectors have the same coin as I then a valuation is possible?
Yes, same coin and same grade, provided there are enough members to generate a value.
If you own rare or extremely rare coins without valuation there is nothing that can be done.
Correct for the Numista generated valuation. You can enter your own value (Buying price).
I have coins that are valuated in the VF and XF sector, but I own an UNC and there is a blank and then nobody can get this coin valued? Or the other way, I owe a coin in VF, but only the XF and UNC are valued.
Until enough members enter Buying price values for their coin/grade, Numista will not generate a value. If you absolutely want to have a Numista generated value then one possible solution is to slide your grade estimate up or down to the closest one with a value. If all the grades have no value then there's nothing you can do other than using your own value.
Maybe I don't explain it correctly or my questions seem odd. I apologize I'm Dutch.
You explained it quite well and not odd at all.