It depends on the bus company you are using. Turbus has its own terminal, Terminal Alameda, in Santiago. Pullman also depart from there. Other buses will mainly use the largerTerminal Santiago across the side road. There are other terminals as well.
The easiest would be to get Turbus to their terminal in Santiago from Valparaíso. When you buy your ticket to Pucón, make sure the bus you book departs from the downtown terminal as they have other departure points in the city. On the schedule it will say "Stgo.T.Alameda TB" (that is: Santiago Terminal Alameda Turbus).
In addition to the excellent advice above, you may wish to avoid the change altogether. Tur-Bus has a departure at 9:30PM from Valparaiso direct to Pucon (no change) arriving at 9:30AM -- it offers both the first-class "salon cama" and the cheaper semi-cama service.
Yes, you should have no problem buying your tickets from any Turbus office. Note that you can get Cama or Semi-cama from Valparaíso. For Premium you need to depart from Santiago.
Thanks. One further question: what's premium? We would like to have comfortable seats that recline. We will get that from Valparaiso?
You can see the different seats here:
The buses with premium seats usually have them on the lower deck of a double decker bus with cama seats upstairs.
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