If I understand your question correctly, you would like to have some external standards which have a constant amount of light peptide in them where the amount of heavy peptide varies according to a calibration curve. In these external standards, you want to use "Ratio to Light" as the normalization method.
Then, in your Unknown samples you want to have the heavy peptide spiked in at a constant level and use "Ratio to Heavy" as the normalization method.
Furthermore, in the Unknown samples you would like to quantify using the heavy peptide's calibration curve.

It might be theoretically possible to do this using Skyline-daily, but I probably would not recommend it. In Skyline-daily we added a new feature which allows you to say that a peptide or molecule should use some other peptide or molecule's calibration curve. You do this by using the Document Grid to set the "Surrogate External Standard" of one peptide to the other.
In order to actually get this to work you would need to trick Skyline into thinking that the heavy peptide that you are using for your calibration curve is a completely different peptide from the light peptide that you are trying to quantify. One way to trick Skyline into thinking that two peptides are completely different would be, in Skyline, to change the peptide sequence so that leucine is replaced with isoleucine. A different way to do this would be to tell Skyline that the peptide sequence has a tiny modification whose mass is 0.0001.

I would probably recommend that you only use your calibration curve to figure out the linear range of your analyte.
Once you have determined that your analyte is the linear range, you would quantify your unknown samples in a separate Skyline document. In that other Skyline document with the unknown samples you would tell Skyline to quantify by multiplying the ratio to heavy by the concentration at which you spiked the heavy peptide in.
The way to tell Skyline which number to multiply by is to set the "Internal Standard Concentration" value in the Document Grid.

I hope this helps.
It is possible that I have completely misunderstood what you are asking.
-- Nick