If you're putting it directly after a passive guitar, you'd want the 250k version. If you put it after a buffer (or buffered pedal- like any Boss pedal), then use the 25k version.
In terms of where you place it, it depends what you want to do. After your guitar but before any dirt pedals or your amp, it's essentially like your guitar's volume control. More volume, more signal into the next pedal or amp. After a dirt pedal (or in your amp's effects loop), it won't change your signal much and be more like a master volume. In front of delay or reverb, you can use it for swells. After delay or reverb, it will control the overall volume of the effects trails.