My fluke is in transit at the moment so no definitive temperature measurements for a couple of days yet. I had previously setup the VII so am comfortable with its temperature but comparative tests with La Valentina will have to wait. That said I couldn't wait at least try out both machines.
You will need to set up a couple of presets on the VII: namely, group temperature, preinfusion time and volumetric dose before pulling your first shots. I won't go into the details here since the steps for setting them are pretty well covered in the manual. I do have some suggestions on starting points that have worked well for me.
Let's start with preinfusion. My recommendation here is 3 seconds with a water inlet pressure of 25psi. I'll be doing a lot more testing of preinfusion later.
Set the volumetric dosing on the double button for 2 oz and the single for 4oz. Why? Because I generally don't pull singles and use that button for back flushing and rinsing. Also I generally pull about 1.75oz doubles so I'll be pretty close even if I'm not paying attention and don't cut the double shot off myself.
Temperature wise 93°C is a pretty good starting point for your basic espresso blends. I picked up some Toscano from Counter Culture Coffee. I am pretty familiar with this blend and lately 93°C has been pulling pretty sweet.
Here's a typical recipe for the VII that has worked for me:
1. Allow the group 25 minutes to warm up.
Or leave it on with the portafilter loosely locked in or use the optional timer to have everything nice a toasty as you're crawling out of bed. Here is a quick picture of the timer control. I'll post more about setting it up later.

2. Draw a blank shot with the portafilter in place.
Press the two-cup button, preferably into your espresso cup to preheat it. You will ultimately have to pull two blank doubles to get the grouphead up to temperature.
3. Measure out and grind your beans.
4. I found that 16 grams of beans (a level basket with one slight tap during dosing) works best for your more traditional espresso blends like Toscano. Lighter roasts have denser beans so will not need the mid dose tap. Some may even end up below the lip for a similar dose.

5. Tamp firmly, about 30 pounds of pressure.
6. Now pull a second blank double. Then lock in the portafilter.
7. Dump the hot water from the cup and wait for the temperature led to stop flashing, wait until it is solid and then press the two-cup button. For me, waiting for the temperature light to go solid is the trick to consistent temperatures across my VII espresso routine.
You will here the water solenoid click on for about 3 seconds before the pump starts followed by your first drops of espresso in about another five seconds and continuing for about another twenty. I like to cut off the pull just as the cone is starting to collapse a bit. This generally just precedes the blonding.
The Toscano worked out pretty well. Nice and sweet strong chocolate notes with just a hint of fruit. I have just started getting the extra fruit in the cup. I think Tim has tweaked the blend a little bit lately. Here is a quick shot of the pour:

Onto Miss Valentina. As I have said earlier I am not very familiar with this machine so I expect it will take me awhile to get used to it. Dan has it set up with one of Eric's thermocouples. Once I get the fluke back it will be a bit easier to dial in the temperature.

Image
For now, I followed Dan's formula in his buyers guide for La Valentina (a brief excerpt follows):
- Allow La Valentina at least 25 minutes to warm up.
- Start the grinder and press the brew button to begin the cooling flush. Remove the portafilter after about 10 seconds, dry out the basket, and then fill and tamp firmly. Again I measured out 16grams of coffee. Dan recommends about 17 grams in his review but I wanted to use the same amount as I had used in the VII.
- Remove the portafilter about halfway through the flush and start to prepare the basket, that doesn't leave a lot of time to dose, distribute, and tamp before you should start the extraction. Listen for the hissing of steam and gurgling of boiling water before locking in the portafilter. Continue drawing water for about five seconds after the stream has settled down, for around six ounces total. Depending on the blend and your taste preference, the recovery time after the cooling flush is somewhere between 15 seconds (puck surface temperature briefly peaks about one or two degrees Fahrenheit above target brew temperature) to 35 seconds (puck surface temperature peaks around four degrees above brew temperature).
- Lock in the portafilter and toggle the brew button to start the extraction.
Remember to relock the portafilter back into the grouphead to keep it warm.
As it turns out things went pretty well after my second attempt. The cone is a bit forward of center on this pour. Note to self - pay more attention to making sure the tamp is level.

The grind was pretty close, surprising given the different basket geometries. The VII is a 53mm basket: smaller diameter but deeper than the 58mm E61 basket. I'm really interested to see if there are taste differences in the two geometries.
Taste wise the Valentina shot was a bit harsher and not as buttery as the VII shot. I suspect my temperature surfing is getting me to a little too high a temperature. I'll have to work on my surfing more and when the Fluke gets back this week I should be able to do a better comparison.