Love, love the Navajo. It doesn't git r dun quite as well as an up engine caravan but it can be a lot more fun to fly. Get good flows down because it is a busy busy airplane. Which is one of the things I like about it.
The following is based on the late model chieftain, with good gear and calco flaps so some or none of it may apply to your bird. If it's a 60s -310, good luck, you're on your own but any of the later model -350s and -325s should be about the same.
Honestly, I don't bother with the hyd pump check other than first trip of the day and last trip of the day.
Takeoff-balls to the walls until 500' then 38" 2400 32 GPH (the POH will tell you that the ABSOLUTE MINIMUM fuel flow at 85% [38/2400] is 30, we've had good luck keeping it higher). If head temps will allow it, climb at the blue line. The sooner you get to cruise altitude, the sooner you can get the power and subsequently the fuel flow down.
I can't emphasize this enough-with the power up the airplane will absolutely devour fuel. It's a characteristic of big turbo recips that they need extra fuel at high power to keep things cool. You can run 75% power (33/2400) all day long but it's loud, burns ~10% more fuel per trip, and the time savings are negligible over the 65% we usually run. I've played around a little bit and if you're not in a big hurry you could even use Amflight power (~26/2200) and really get fuel flows and engine temps down with a nearly negligible change in block time. All that said 90% of my cruise time has been spent at 30"/2200/18 GPH per side. One point that I do agree with Pat on is to ballpark a block fuel burn of 40 GPH, at least until you get the time in that airplane and your engine management down to where you have the feel of your airplane and operation.
As far as cruise altitude, depending of course on winds and stage length, 5500/6500 are generally the most efficient.
For descent planning, here is what I do.
VFR: same as Pat, altitude times two is minutes out to start your 500 fpm descent. Plan 2" of MP reduction every 2 minutes (making a change smaller than 2" MP can be difficult, the turbos can be just a bit touchy) and plan to hit the airport at 24" MP. If you're following so far, that means I'm typically making my first power reduction to 28" at 6 minutes out, 26" at 4 minutes out, etc. this profile puts you in a good spot to level at pattern altitude and into flap then gear then more flap range (do you have the 162 knot flaps and 153 knot gear?). VFR pattern flaps 15 on they downwind, gear down abeam touchdown and run a gump check (gas [tanks and pumps] undercarriage mixtures set [dont usually touch them between setting cruise power and shutting down on the ramp, unless I have to do an extended level off for spacing or whatnot] props 2400) then flaps full turning final. A lot of guys like to eke the flaps in like 2* at a time, that is a good idea with the dukes flaps but stupid and unnecessary with the calcos. Look for about 100 down final and 90 crossing the threshold, I've always found she lands real nice with full flaps and idle power. Careful to let the nose down easy while you still have some speed and elevator authority, otherwise she'll slam down.
IFR descent profile is similar to VFR, except plan everything to the FAF instead of the airport, and put flaps 15 in established on the FAC. That should put you at 24" and min altitude at the FAF, at which point you should be able to drop the gear, then depending on when you break out flaps full when you have the runway in sight. Easy peasy.
Two things I can't emphasize enough: first, you have to think ahead when you're flying this thing or it will eat your lunch. The handling characteristics are amazingly docile for a cabin class twin, especially if you have the VGs, but it is just fast enough to bite you especially if you are coming from a 172 or similar. Second, your maintainers really, really need to know what they're doing. There are a million little gotchas that can really ruin your day on this machine, from the exhaust system (AD mandates an inspection every 60 hours) to the gear (one little oversight there led us to slide ours in on the nose, oops). Even the things that won't bite you hard can get gremlins that will either AOG you or just drive you and your mechanics crazy.