Are you asking how you can measure the effect of BSA on binding of a ligand to DNA? First, you need to have a method for measuring the binding of the ligand to the DNA. There are many possibilities. Preferably, you will use a quantitative method that allows you the measure the dissociation constant, Kd. The best method depends on the nature of the ligand and the techniques and equipment that are available to you.
Then, you add various concentrations of BSA and measure the DNA binding affinity of the ligand again. You can quantify the inhibitory effect of the BSA as the concentration required to inhibit DNA binding by 50% (IC50).
The answer is the same if you are interested in measuring the effect of DNA on binding of a ligand to BSA, just switching the BSA and DNA in the above explanation.