If you're keen to train 5 days a week, the standard approach to that for bodyvuilding would be something to the effect of:
Day 1: Legs
Day 2: Chest
Day 3: Back
Day 4: Shoulders
Day 5: Arms and abs
I prefer an upper/lower split over a 5-day body part split, but I'm not very big, so take from that what you will.
All of the machines have their purpose. Every exercise has its use. So I'm not going to tell you what's "best." But I will give you some quick recommendations, using the 5 day spit formula from above:
- Start each day with a free weight, compound exercise. Free weight means dumbbell, barbell, kettlebell, any other kind of -bell you can think of, or cable machine. These exercises do not have a fixed motion. Compound means that multiple joints are moving (and are meant to move) throughout the range of motion, so for a lower body exercise your hips and knees are both moving, and for an upper body exercise your shoulders and elbows are both moving. Examples: squats, lunges, deadlifts, bench press, dips, shoulder press, pull ups, most variations of rows.
- As the workout progresses, you may wish to move across to machines (other than cable machines) or isolation exercises (exercises that move around a single joint and really focus on a specific muscle group). As you progress in this direction, the need to stabilise yourself decreases, as does the demand for technical skill. Barbell squats are a very general, technical exercise; leg presses are more focused on the legs and less technical; leg extensions and leg curls have very little technical demand and really hammer the quadriceps and hamstrings respectively.
Even on the exercises that don't require much technical focus, you do still want to focus on the technique points that are there to maximise your muscle contractions while minimising the risk of injury. The temptation to load up more weight than you can handle with good technique will often be there, but your ability to handle the weight should always be a measure of how much weight you use. The cool thing is that good technique makes you stronger faster and more reliably than bad technique, so in a way that desire is fulfilled longterm by overcoming the short term temptation.
As a beginner, you tolerance for both intensity and volume will be low. The good news is the stimulus required to push progress will also be low, so it all works itself out if you're sensible. Let's say you do 4 exercises per workout. Starting out, you might only do 2 working sets of each, and since technique will be your measure rather than how much weight you can possibly lift, you'll finish each set feeling like you could have done more. That's a total of 8 low intensity work sets per day. Not a lot. At this stage, your most intense sets will probably be at the end, as you use really simple exercises at that stage, and so technique failure won't happen too far ahead of muscular failure. Still, doing that, drilling technique so that you can push yourself a little bit further each week, and eating sufficiently, will get you good results over time.
Eating sufficiently. There's a lot of bad advice out there on nutrition, because people get obsessed with the scale and want to either gain or lose weight as fast as possible, under the delusion/false hope that everything they gain/lose is what they wanted to gain/lose. In reality, you can gain maybe 10kg of muscle in your first year of training, which is about 20lb, which is less than 2lb/month, which means that a see food diet is probably not a great idea. The flip side to that is that if you aren't gaining 2lb/month, you're probably not gaining as much muscle as you could, and therefore you'll want to increase the amount you consume each day to make that happen. My recommendation is to immediately add 200kcal/day into your diet (preferably from healthy food sources -- health should always come before size/strength), and, so long as you're training for hypertrophy, check your weight under the same conditions each week (I suggest first thing in the morning after alleviating your system, stark naked without eating or drinking anything beforehand, same day of the week). If after 2 weeks you haven't gained 1lb, add another 1-200kcal into your diet. If you've gained more than 1-1.5lb, take 1-200kcal out of your diet. Keep modifying your diet as you progress -- what causes you to gain weight now might be maintenance for you in a month's time, as your body adapts to different training and nutritional conditions.