Silver particles have been prepared by reduction of silver nitrate with ascorbic acid in acidic aqueous solution containing a low concentration of a commercial polynaphthalene sulfonate polymer (Daxad 19) as dispersant agent. The reduction has been induced and controlled by the slow addition of ascorbic acid at a fixed rate; in this way, we were able to monitor the formation of a silver crystalline colloidal dispersion by in situ and time resolved Small Angle X-ray Scattering measurements. Modeling the scattering intensity with interacting spherical particles in a polymer-Ag like-fractal template allowed us to distinguish different stages involving liquid-like ordered cluster nucleation, cluster growth up to primary particle formation and particle coalescence. Between primary particle formation and particle coalescence, we observed the occurrence of a transient phase of core-shell type structures having primary particles as stable cores in expanding shells built by the organic polymer. We discuss these results in a twofold perspective pertaining both to technology, relative to controlled fabrication of metal nanoparticles and to basic chemical physics, dealing with non standard stepwise crystallization from solutions.